WO2024043132A1 - 固体潤滑被膜を形成するためのコーティング用薬剤、そのコーティング用薬剤の製造方法、油井管補修方法、油井管の潤滑改善方法、及び油井管 - Google Patents
固体潤滑被膜を形成するためのコーティング用薬剤、そのコーティング用薬剤の製造方法、油井管補修方法、油井管の潤滑改善方法、及び油井管 Download PDFInfo
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- WO2024043132A1 WO2024043132A1 PCT/JP2023/029434 JP2023029434W WO2024043132A1 WO 2024043132 A1 WO2024043132 A1 WO 2024043132A1 JP 2023029434 W JP2023029434 W JP 2023029434W WO 2024043132 A1 WO2024043132 A1 WO 2024043132A1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/02—Water
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/05—Metals; Alloys
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/0215—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/055—Particles related characteristics
- C10N2020/06—Particles of special shape or size
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/34—Lubricating-sealants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/015—Dispersions of solid lubricants
- C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/023—Multi-layer lubricant coatings
- C10N2050/025—Multi-layer lubricant coatings in the form of films or sheets
Definitions
- the present disclosure provides a coating agent for forming a solid lubricant film, and a technique suitable for repairing a threaded portion of an oil country pipe and improving lubrication performance using the coating agent. That is, the present disclosure is a technology related to lubrication of a metal surface of a metal component such as an oil country pipe screw using a solid lubricant coating.
- the present disclosure is used, for example, when lubricity that is one level higher than existing solid lubricant coatings is required. That is, the present disclosure also includes coating on an existing solid lubricant coating for the purpose of improving lubricity and preventing seizure, including in a preventive sense.
- the present invention also covers the case where lubrication is achieved simply by using the solid lubricant film of the present disclosure.
- the present disclosure relates to the lubrication of threaded joints for oil country tubular goods, for example, in the case where mild seizure occurs only in the threaded part of the threaded part and the seal part that make up the threaded part, which is a component of the threaded oil country pipe. used for.
- the present disclosure relates to a chemical that is intended to be cured by scraping the burnt-in area with a grinder, sandpaper, file, etc., and then applied to the area for partial repair on-site. Partial repairs are also called touch-ups.
- wet lubricating compounds have been used to lubricate the threaded parts (joints) of oil country tubular goods used at oil and gas drilling sites and production sites, where they are tightened and untightened.
- Lubrication using lubricating compounds is still the mainstream.
- the oil country tubular goods are made of carbon steel
- a Mn phosphate chemical conversion film is formed on the threaded surface as a base.
- an electroplating film such as Cu plating is applied to the thread surface on the box thread (female thread) side.
- a lubricating compound is applied to either or both of the box thread and the pin thread to provide lubricity.
- Lubricating compounds have traditionally been compounds made of grease, etc., containing heavy metal groups such as Pb, Zn, and graphite. Currently, there are environmentally friendly compounds that do not contain such heavy metals, and they are already in use. Furthermore, although it is not yet mainstream, lubrication technology using a dry solid lubricant film is also being used. Wet compounds form a wet lubricating film. On the other hand, lubrication technology using solid lubricant films is called dry technology or greaseless technology. Lubrication technology using solid lubricating films is becoming one of the important technologies that can achieve the lubrication of oil country tubular goods used in oil/gas drilling sites and production.
- a touch-up partial repair
- touch-up is performed on mildly burned areas of the thread region of a box screw or the thread region of a pin screw.
- the damaged area and its surroundings are ground and cured using a grinder, sandpaper, file, etc.
- the underlying film such as the Mn phosphate chemical conversion treatment for lubrication purposes and the electroplating layer disappears due to curing. For this reason, it has conventionally been attempted to maintain lubrication by applying commercially available lubricating paste, lubricating spray, or the like to repair the seal portion.
- Molykote manufactured by Dow Corning and DuPont
- Molycoat itself is a brand name.
- molycote does not necessarily contain MoS2 , but there are also products that mainly contain Zr-based, F-based, and graphite, or products that contain a mixture of them.
- molycote refers to one mainly containing MoS2 .
- Molycoat and its similar product group may also be collectively referred to as Molycoat.
- Lubrication of oil country tubular threads can also be achieved with Molykote and other anti-seize sprays or pastes by themselves. However, they are expensive. For this reason, it is also not common practice to achieve lubrication of oil country tubular threads by applying it in a work yard near the well or by itself at the well tightening site.
- Molykote is normally used in the field of oil country tubular goods as follows, only when lubrication is abnormal. That is, the common usage is to apply Molycoat to the pipe during touch-up at the wellhead after curing the burned-in area at the site of tightening the well.
- Molykote is a lubricant that guarantees a high level of lubricity, and is not something that can be used to completely fill the repaired area with putty. Molykote is only a repair material.
- Molycoat as used herein mainly contains MoS 2 and an oil-based solvent such as mineral oil (organic solvent-based) to synthetic oil. That is, Molycoat is composed of mineral oil such as white mineral oil, PAO (polyalphaolefin), PAG (polyalkylene glycol), etc., in which MoS 2 is dispersed and blended. A spray or paste form of Molycoat is then typically applied to the repaired area.
- White mineral oil is a baby oil that is a colorless liquid and non-volatile stable oil at room temperature.
- some Molykote is made by mixing lithium soap or calcium soap as a thickener with the base mineral oil to give the oil viscosity.
- a screw with a burned-in thread area is made usable again by touch-up at the wellhead.
- Apply molycote to the entire surface of the threaded part and tighten it.
- a lubricating compound (API-Mod, etc.) may be applied to the entire surface of the threaded portion and tightened again. In this case, wait for the mineral oil to dry before using the lubricating compound.
- This touch-up at the wellhead is a remedy for mild seizures in the thread area, with the aim of maintaining the sealing properties of the thread.
- Molycoat may be applied as a preventive measure to improve the overall lubricity by one rank.
- Non-Patent Document 1 describes a report that when a lubricant consisting of a spray containing MoS 2 was applied to an oil country tubular product made of a Ni-based alloy, the pipe cracked.
- the lubricating compound is a viscous liquid paste. Therefore, the compound moves in conjunction with tightening and loosening.
- solid lubricant coatings do not have this problem and are inevitably slightly scraped by tightening and loosening. Furthermore, it cannot be expected that the fragments and peeled pieces originating from the solid lubricant coating itself will always move in conjunction with tightening and loosening. If these secondary products, such as fragments, get stuck in the thread gap, seizure will develop. For this reason, touch-up at the wellhead is still considered important even when using solid lubricant coatings for lubrication.
- the solid lubricant film is a dry solid lubricant film, which is called a dry film.
- Molykote is dissolved in mineral oil to synthetic oil solvents such as white oil, PAO, and PAG. For this reason, the film formed with Molykote is often slightly wet rather than completely dry. Therefore, Molykote does not meet the technical concept of a dry solid lubricant coating. Strictly speaking, Molycoat does not fall into the technical category of solid lubricant coatings, which are premised on being ⁇ dry.'' Even when Molycote is in spray form, it can sometimes be treated as a dry coating once it dries. However, in many cases, solid lubricant components and binder resin components are mixed into white oil-based solvents, which takes time to dry. Even if you wait a long time for it to dry, it will often remain semi-wet and not completely dry.
- a Mn phosphate chemical conversion treatment film or an electroplating film is applied as a base to the box thread (female thread) side.
- a lubricating compound is then applied to the lubricated surfaces between the threads to achieve lubricity.
- the lubricating compound is a viscous liquid paste, and moves in conjunction with tightening and loosening. Therefore, the influence of the size of the oil country tubular goods is not large, and excellent lubrication can be expected.
- solid lubricant coatings are strongly influenced by the outer diameter and wall thickness of the oil country tubular goods.
- lubrication is achieved by the solid lubricant film itself being scraped away little by little.
- the membrane is often damaged due to misalignment during tightening, or when a shock is applied to the coupling screw (female thread) when the pin screw (male thread) is initially inserted and set.
- lubrication using solid lubricant coatings generally tends to cause seizure.
- the tightening torque value increases and the weight of the pin screw also increases. Therefore, in an actual field where the product is tightened while being hung upright, damage such as the solid lubricant coating being completely peeled off may occur.
- the overall structure of the solid lubricant film is a two-layer film structure.
- the case where the base film is not considered is, for example, the case where the phosphorylation treatment film or the electroplated film is not considered.
- Patent Documents 1 and 2 describe the overall two-layer membrane structure and partial membrane reinforcement.
- This patent document describes a part that has a two-layer structure for the purpose of partially reinforcing it, particularly a part targeted at the shoulder part. That is, as a part having a two-layer structure, an example in which the surface layer side has high hardness (Patent Document 1) and an example in which the surface layer side has a high coefficient of friction (Patent Document 2) are disclosed.
- Patent Document 1 and 2 There are also many examples of full two-layer structures.
- Patent Documents 3 and 4 can be cited. These are two-layer structures throughout.
- Patent Document 3 a solid lubricant film containing no solid lubricant (only binder resin) is formed on the surface layer, and a normal solid lubricant film containing a solid lubricant is formed on the lower layer.
- the two-layer structure in Patent Document 3 covers the point where the solid lubricant film becomes porous and lacks rust prevention ability due to the solid lubricant, with the outermost layer (solid lubricant film without solid lubricant). . In this way, Patent Document 3 aims to improve the corrosion resistance ability.
- Patent Document 4 by forming a viscous liquid lubricant layer in the lower layer, it moves in conjunction with tightening and loosening, like lubrication with a conventional compound. In this way, Patent Document 4 aims to make it possible to constantly maintain lubrication in a self-repairing manner.
- the upper solid lubricant film serves as a cover for the lower viscous liquid lubricant layer. Furthermore, the upper layer solid lubricant coating is easily destroyed when extremely strong surface pressure is applied, and forms a lubricant layer integrally with the lower layer.
- the hardness of the layers is such that the upper layer is hard and the lower layer is soft, and these layers provide most of the lubricating function.
- Patent Documents 5 to 7 there are techniques described in Patent Documents 5 to 7.
- Patent Document 5 exemplifies that an acrylic silicone resin is formed on a UV cured film, and that the acrylic silicone resin contains a metal soap as a solid lubricant.
- lacquer-based spray-type acrylic silicone resin water-based and oil-based resins are exemplified, and it is described that oil-based resins are good. That is, a water-based binder resin is not actively used.
- Patent Document 6 describes that it has a viscous liquid or semi-solid lubricating film and a dry solid film formed thereon, and that both films contain a solid lubricant.
- Patent Document 7 exemplifies an acrylic resin as a thermoplastic resin.
- non-volatile components include metal soap and wax, for example. It is also described that wax is effective not only for anti-seizure effects but also for reducing the fluidity of the composition for forming a lubricating film and improving the film strength. It is also stated that animal waxes, vegetable waxes, mineral waxes, and synthetic waxes can all be used.
- Patent Documents 8 and 9 examples of conventional techniques that take into account tightening in actual wells include Patent Documents 8 and 9, Non-Patent Document 2, and the like.
- Patent Document 8 clearly states that the initial set was tested at an angle of 6 degrees using vertical power tongs and assuming misalignment, using short pins of 7" size.
- the length of the short pin in this specification refers to the general length of the pin used for the API RP 5C5 2017 thread test. Specifically, its length is approximately 1 m.
- Patent Document 9 describes an example in which misalignment was tested and evaluated at 5 degrees using vertical power tongs and short pins of 9-5/8" size.
- Non-Patent Document 2 discloses that using vertical power tongs, a weight of 5 kN (approx. This paper evaluated lubrication.
- the metal soap referred to in the present disclosure is a salt of a metal ion other than an alkali metal and a higher fatty acid.
- Alkaline soap is a so-called soap that is used on a daily basis, and is defined as a salt of Na ion or K ion among alkali metal ions and higher fatty acid. Salts of alkali metals other than Na and K are treated as metal soaps.
- the present disclosure will further consider the case of a drug that is based on an aqueous solvent.
- the aqueous solvent refers to a solvent whose main component is water.
- the metal soap itself is water-repellent and insoluble in water, so it is said to be difficult to mix with an aqueous solvent.
- Metallic soaps are also said to be insoluble in alcohols.
- VOC volatile organic compounds
- this group of drugs is classified into toluene, xylene, benzene, VOC group belonging to mineral spirits, ether group, and oil, which is widely called mineral oil, which are often considered harmful to health. Are known.
- metal soap is prepared by dissolving the metal soap itself in the above-mentioned VOC and then turbidly mixing it with a solvent mainly composed of water.
- VOCs When water evaporates and evaporates, VOCs also fly away. Therefore, as a result, it becomes possible to disperse metal soap in a water-soluble or water-dispersible polymer.
- Patent Documents 5 to 7. In consideration of worker safety and the environment, and in areas where open flames are strictly prohibited, there is a high possibility that the group of chemicals called thinners cannot be used because they evaporate.
- An example of a place where fire is strictly prohibited is an oil/gas drilling environment.
- a water-based (water-soluble or water-dispersible) polymer refers to a polymer in which the main component of the solvent is water, and when applying a drug to form a film, this water component must be removed by drying.
- Water-based polymers use water as a solvent, so when drying, there is a method of heating the object to be coated, or conversely, warming the position of the object to be coated before applying. In either case, if there is no process that promotes water volatilization and evaporation, long waiting times will occur for drying, resulting in inefficiency. However, in the case of touch-up at the wellhead, since the area is strictly prohibited from using fire, it is desirable to be able to dry it simply by leaving it alone without using a heater or the like.
- drying environment using a compressed air-based blower which is often supplied at the wellhead, can be expected, so drying using that may also be considered.
- the drying environment is, for example, a situation where the ambient temperature is + (approximately 5° C. to 10° C.).
- Patent Document 5 states that an oil-based acrylic silicone surface film is preferably selected because it becomes a dry film in a short time at a relatively low temperature.
- Patent Document 5 is an example in which the volatilization of an oily solvent is utilized to achieve early drying without selecting an aqueous solvent.
- Patent Document 6 exemplifies a system using only a water system, a system using water + a volatile organic solvent, and a system using an ultraviolet curing resin. Among these, the latter two points can be dried early.
- Patent Document 6 does not clearly disclose the method.
- Patent Document 7 discloses a method to speed up the drying time by using a volatile solvent and a chemical with a flash point of 30° C. or higher.
- a volatile solvent and a chemical with a flash point of 30° C. or higher.
- the flash point is around 30° C.
- a risk factor such as a spark in hot regions such as desert areas in the middle of summer.
- Materials with low flash points that is, materials that are easily flammable, have the problem of increasing the risk of fire and other accidents unless they are used in a well-controlled environment. In other words, how to dry safely and quickly is still an issue.
- VOC volatile organic compounds
- thinners toluene, xylene, benzene, and other organic solvents
- VOC volatile organic solvents
- fluorine-based solvents such as fluorocarbon substitutes
- fluorine-based resins which can be dissolved in them and used as binder resin components in paints.
- fluorine-based compounds have been treated as the king of surface treatments because they dry quickly and have excellent lubrication and anti-corrosion properties.
- fluorine-based compounds can no longer be used. Under the U.S.
- PFAS fluorine compounds
- drugs and products that can be used with fluorine are exempted from TSCA, including Teflon (registered trademark) (PTFE: polytetrafluoroethylene), PFPE (perfluoropolyether), and fluorine-based solvents.
- PTFE Teflon (registered trademark)
- PFPE perfluoropolyether
- fluorine-based solvents including but only HFE (hydrofluoroethylene) is available. Furthermore, the international trend toward designing solid lubricant coatings without the use of fluorine can no longer be ignored.
- the reason for this is that the rental cost of the power tongs itself, which is a tightening device, is enormous, and it is necessary to proceed with as many installations as possible without any problems.
- the above-mentioned touch-up refers to partial repair of burned-in areas at the wellhead.
- Patent Documents 1 to 3 highly volatile organic solvents with low or likely low flash points are used in order to quickly form a film. That is, the coating agent is designed with the assumption that it will be produced and transported away from the oil/gas well. Agents based on chemicals with low flash points are extremely dangerous to use near oil/gas wells where open flames are prohibited. Furthermore, the evaluation of the lubrication properties by touch-up at the wellhead is not at a level that can be evaluated by conventional simple laboratory experiments or simulations. For this reason, it is preferable that the evaluation of the lubrication properties by touch-up at the wellhead be set so as to be able to cope with even the most severe conditions imaginable.
- the viscous liquid lubricating compound commonly used for conventional lubrication of OCTG threads is not suitable for evaluation of tightening and untightening using short pins in the laboratory and for actual well conditions. There seems to be no difference.
- the viscosity of liquid lubricating compounds tends to be evaluated in wells according to laboratory evaluations. This is because the lubricating compound has a liquid viscosity, so it is assumed that the compound moves in conjunction with the tightening and loosening process.
- a solid lubricant coating when a solid lubricant coating is used, the fragments derived from the solid lubricant coating that are unavoidably shaved off during tightening and unfastening do not necessarily move in conjunction with each other.
- An incompletely threaded portion is, for example, a place where the thread is not perfect and the thread height and thread root are small.
- the lubricant when lubricating oil country pipe threads with a lubricating compound, the lubricant has a liquid viscosity. Because of this, it can move in conjunction with tightening and untightening, which is a good contrast to the fact that the laboratory lubrication evaluation method using short pins and the results in actual wells are almost the same. In other words, this is a problem unique to solid lubricant coatings.
- FIG. 3 The tightening/retightening test conditions shown in FIG. 3 are an example in which the bolt was rotated at 15 to 25 rpm until torque was established, and then rotated at 2.5 to 1.5 rpm once torque was established. This is the result of testing under severe conditions, such as high rotational speed, beyond the conditions specified in the screw instruction manual (tightening instructions in the technical package).
- the well tightening material/strength grade was a 9-5/8"53.5# Q125 material and a JFELION TM screw designed to have lubrication with a solid lubricant film.
- Fig. 2 shows a screw of about 1 m long.
- the former condition refers to a situation where the pin screw is short and easy to handle, the pin screw can be set straight, and the pin screw thread can be manually set until it is hidden by the box screw.
- the condition refers to a situation where a box screw is installed with a long pipe with a pin screw placed horizontally, and the short side is set, so the box screw can be set straight without any axis misalignment.Pin The reason why the torque builds up immediately from the beginning of rotation is because the pin screw and box screw are sufficiently engaged at the initial setting stage.
- the horizontal axis in Figure 2 is approximately 1.5 rotations.Also, Figure 2 This is an example where the tightening start position with power tongs was manually tightened.
- FIG. 3 is a torque turn chart for Range-3, that is, one actual length pin of over 40 feet (over 12 m).
- Figure 3 shows the results of a test conducted in a simulated well. The unit (size) of the horizontal axis is different from that in FIG.
- a simulated well is not a well that actually produces oil or gas, but is an experimental well in which a hole is simulatively opened so that a full-length pin can be tightened and tightened.
- a simulated well means a group of equipment and experimental facilities that have such a configuration and can perform tightening and tightening tests.
- FIG. 3(a) is the torque turn chart. This example shows a tendency in a setting similar to that in an actual well. However, unlike the case of the short pin shown in FIG. 2(a), the case shown in FIG. 3(a) has a characteristic in which no torque is generated and the pin is idling. In the example shown in FIG.
- Patent Documents 8 and 9 are evaluations using short pins.
- Non-Patent Document 2 is a paper that evaluates lubrication by using vertical power tongs and placing a weight of 5 kN on the upper end of a short pin. Judging from the torque turn chart of a 7"29# pin, Non-Patent Document 2 intends to apply the weight of one actual length pin, that is, about 40 feet (about 12 m). However, judging from the torque turn chart, the tightening behavior is closer to that shown in Fig. 2(a), rather than that shown in Fig.
- the initial set position is manual tightening with a pin screw.
- the test is determined to be a tightened evaluation test when the pin screw and box screw are fully engaged with each other until they are tightened to a level that does not expose them. Not yet.
- the present invention was made with attention to the above-mentioned points, and is a coating agent that does not use MoS2 , is environmentally friendly, and can be applied to actual wells as a coating agent for repairing oil country pipe threads and improving lubrication.
- the aim is to provide drugs that can withstand use in
- the present disclosure is directed to oil country tubular thread lubrication techniques using solid lubricant coatings.
- the present disclosure is applicable, for example, to lubrication of threaded joints for oil country tubular goods, and for repairs performed at the wellhead when mild seizing occurs only in the threaded parts of the threaded parts and seal parts of the threaded oil country tubular components. It is related to the drug used.
- the present disclosure relates to, for example, a chemical that is applied to the burned-in area, including the cured area, for the purpose of touch-up after the burnt-in area is ground and cured with a grinder, sandpaper, file, etc.
- the present disclosure also aims to improve lubricity by forming a top coat with the agent of the present disclosure when lubricity that is one level higher than the solid lubricant coating that has already been formed is required. That is, it includes coating on the existing solid lubricant coating for the purpose of preventing seizure, including a preventive meaning.
- the invention of the present disclosure was made by extracting problems from the above-mentioned prior art group and considering the following conditions.
- the ingredients are designed without using MoS2 as a chemical, which is concerned about its correlation with cracking. From the viewpoint of ecology, worker safety, and the ability to be used even when open flames are strictly prohibited, the drug is designed based on water-soluble substances. At the same time, the solvent water can be dried quickly to form a film. Solid lubricants do not contain harmful heavy metals such as Pb. In addition, we do not use any chemicals containing PFAS (fluorine-containing acrylic groups, including PFOS and PFOA) or alternative fluorinated solvents with high global warming potential as constituent elements of the binder resin.
- PFAS fluorine-containing acrylic groups, including PFOS and PFOA
- alternative fluorinated solvents with high global warming potential as constituent elements of the binder resin.
- the present disclosure is designed to incorporate graphite and metal soap as solid lubricants into a water-based polymer.
- Graphite and metal soap are said to be insoluble in water, but slightly soluble in alcohol.
- graphite and metal soap are dissolved in alcohol by dissolving the graphite and metal soap in advance and then mixing the mixture with a water-based polymer stock solution. Otherwise, graphite and metal soap cannot be uniformly dispersed in a water-based solvent. In addition to homogeneous dispersion, we also clarified the necessary content for lubrication and early drying.
- the inventor discovered that when graphite is used as a solid lubricant, during tightening and unfastening, the graphite as a solid lubricant becomes integrated with the binder resin, and stretches for a long time, forming a tape-shaped secondary product. We have obtained knowledge that this may occur. The inventor has found that this tape-like secondary product increases the risk of burn-in. Therefore, even if lubrication is assisted by combining the binder resin of the present disclosure with a solid lubricant of metal soap, if the lubrication of graphite is utilized, the tape-shaped secondary product will not be caused to seize. This suggests that there is an appropriate amount to add.
- a water-soluble or water-dispersible polymer is used, and a solid lubricant is dispersed and distributed in a binder resin that becomes a soft polymer resin film when the film dries.
- a solid lubricant is dispersed and distributed in a binder resin that becomes a soft polymer resin film when the film dries.
- metal soap and graphite are mixed together as solid lubricants.
- the graphite includes a portion that is held together with the polymer and a portion that is not fully retained by the polymer and is exposed as a single graphite and plays a role in lubrication.
- the graphite works together with the lubrication of the metal soap to maintain lubricity.
- Graphite is widely used as a lubricant.
- a structure with grooves such as an oil country pipe thread, and in the situation of a dry film such as a solid lubricant coating, when the lubricating component graphite is pressed and deformed, there is an escape route (direction of elongation and deformation). )" are limited.
- the present disclosure is a water-soluble or water-dispersible polymer that is used as a membrane after removing water.
- dry environments are the main focus.
- the polymer material of the binder resin and graphite constituting the solid lubricating film may form a black tape-like shape in a constrained state such as a thread groove, which may cause seizure.
- graphite is used as a solid lubricant, but during tightening and unfastening, the graphite as a solid lubricant becomes integrated with the binder resin and expands into a long tape-like secondary product.
- ingredients that are different from past ideas.
- the ingredients are designed to not only increase lubricity but also fill in the repaired areas.
- the solid lubricant coating and chemicals of the present disclosure are evaluated to determine their suitability and upper and lower limits for parameters using an evaluation method that is suitable for the environment in which they are actually used in wells. This provides a chemical and a solid lubricant coating that can be used in actual wells and can provide lubrication assistance or repair mild seizing areas.
- the goal that can be achieved with aqueous systems is to have an early drying performance that allows drying within 30 minutes, preferably within 15 minutes, and more preferably within 5 minutes when left at room temperature.
- Patent Documents 5 to 7 describe the use of highly volatile organic solvents to achieve early drying properties. However, it cannot be used in the environment assumed in this disclosure. Further, for ultraviolet curing resins as disclosed in Patent Document 5, this means that a device capable of irradiating ultraviolet rays is required at the wellhead.
- the present disclosure preferably dries within 5 minutes, preferably within 3 minutes, and more preferably within 1 minute. To be able to cope with the usage situation at the wellhead and the usage situation on the production line without slowing down the line speed. Therefore, in order to dry within the takt time of the production line, early drying is also an objective.
- the present disclosure is designed to contain graphite and metal soap in a water-based polymer, particularly a water-based acrylic film or a water-based methacrylic film.
- metal soaps are said to be insoluble in water and insoluble in alcohol. For this reason, it is necessary to devise ways to mix the metal soap into the water-based polymer stock solution in a nearly homogeneous state.
- graphite when graphite is used as a lubricant by itself, it is mixed and dispersed with appropriate additives in a solvent such as a water-based soluble or oil. Therefore, in order to design a drug by homogeneously dispersing it in a solvent mainly composed of water, it is necessary to take similar measures to make it soluble in an aqueous solvent, just as with metal soaps.
- Patent Documents 5 to 7 are examples of promoting the volatilization of water-based solvents by mixing them with thinner-based VOCs and utilizing their volatility.
- thinner-based organic solvents we aim to enable use in an environment where fire is strictly prohibited at the wellhead under the most severe usage conditions, so we assume that thinner-based organic solvents will be used in methods based on these ideas. do not.
- the tape is in the form of a tape, it should be short and piecemeal, preferably in powder form, with graphite scattered throughout.
- the solid lubricant made of graphite is uniformly transferred to the box screw and pin screw.
- the powder or small fragments derived from the solid lubricant coating are moved in conjunction with tightening and unfastening, and the screw gap is closed. Make sure it doesn't get clogged. This state can be stably achieved even when graphite is selected as a solid lubricant.
- Patent Documents 1 to 4 which have a two-layer structure when unused.
- the present disclosure does not necessarily correspond to a two-layer structure in which the outermost layer is partially reinforced with a hard film, or a high-strength film is placed as the top layer to protect the viscoelastic film below.
- These methods cannot solve the problems intended by the present disclosure.
- some parts may also have a two-layer structure, but the application fields are different.
- conventional techniques such as commercially available lubricating sprays in which there is no binder resin and only a lubricant is placed on the outermost layer have a different concept from the present disclosure.
- a solid lubricant is incorporated into the film in the presence of a soft binder resin. At the same time, it also includes a situation in which another type of solid lubricant film is present in addition to the binder resin. This technology is different from conventional lubricant sprays and the like.
- Patent Documents 8 and 9 are the results of tightening tests using short pins with misalignment set at 5 or 6 degrees. However, this seems to be a case where the test was not realistically severe. Pass/fail evaluations using these methods do not always work. In fact, when a short pin is used to perform a tightening and unfastening test with misalignment of 5 or 6 degrees, the following is assumed. That is, the inclination of the pin screw is determined by the loose fitting margin of the incomplete thread of the box screw or the tapered tip of the pin screw. For this reason, it is difficult to set and insert the screw at 5 degrees or 6 degrees due to the structure of the screw. As shown in FIGS.
- the screw has a taper. Initial rattling occurs only due to slight differences in screw engagement, and 5 to 6 degrees is unrealistic. The threads on the male thread (pin) and the thread on the female thread (coupling) hit each other midway through. Therefore, due to the structure, it is absolutely impossible to tilt up to the taper angle of the screw thread. At the same time, even if you can do it for a moment, you won't be able to sustain it for more than a few rotations. After tightening it several times by hand, the pin screw will stand up and be set straight. Therefore, the conditions are not particularly severe, with only the initial momentary moment at the tip of the pin screw and the middle area between the box screw being severe.
- FIG. 5 is a typical example of a situation in which a full-length pin, approximately 40 feet ( ⁇ approximately 12 m) long, is set.
- the pin is long and heavy. For this reason, even if you use a compensator or stubbing guide and lift it with a derrick crane, the actual length pin cannot be set vertically.
- the pin was set slightly bent, and after just a few turns of hand-tightening, it got stuck in the middle and wouldn't go any further.
- the forced rotation from the state shown in FIG. 5 to the state shown in FIG. 4(b) occurs in an actual well. Unless this is simulated and evaluated, it cannot be said that the upper and lower limits of the parameters can be defined correctly. This is common to past prior literature. In order to give meaning to the specified range, it is necessary to evaluate lubricity using a new evaluation method that can perform simulations based on tightening and tightening in an actual well, a simulated well, or a simulated well.
- the present disclosure is a coating agent in which a water-soluble or water-dispersible polymer (water-based polymer) is a binder resin, a solid lubricant is a mixture of metal soap and graphite, and a solvent is water as a main component.
- the present disclosure provides, for example, a case where mild seizure occurs in only the threaded portion of the threaded portion and the seal portion of the component (threaded portion) of the oil country tubular thread during lubrication of an oil country pipe threaded joint.
- It is a repair technology. That is, the present disclosure is a repair technique used for repair at the wellhead. Cure the burnt-in area by scraping it with a grinder, sandpaper, file, etc. Thereafter, the area, including the curing area, is repaired by applying the agent of the present disclosure for touch-up purposes.
- the present disclosure relates to an oil country pipe threaded joint in which a drug is formed into a film.
- the main components of the present disclosure are a water-soluble or water-dispersible polymer (water-based polymer) composed of a binder resin, a solid lubricant composed of graphite and a metal soap, and water as a solvent.
- the binder resin is mainly a water-based acrylic resin or methacrylic resin.
- water-based acrylic resin and methacrylic resin will be referred to as water-based acrylic resin.
- the present disclosure aims to improve lubricity when the lubricity of a solid lubricant coating is required to be one level higher. Alternatively, the purpose is to avoid burn-in, including as a preventive measure.
- the present disclosure also includes techniques for applying over the existing solid lubricant coating to form a top coat for such purposes.
- the present disclosure assumes that the metal soap is homogeneously mixed in the coating agent. That is, it is based on the premise that a metal soap that is originally water-repellent and insoluble in water can be prepared in a homogeneous manner.
- the drug is designed not to contain MoS 2
- the film after drying is also designed not to contain MoS 2 .
- mineral oil-based to synthetic oil-based white mineral oil, PAO (poly- ⁇ -olefin), PAG (polyalkylene glycol), etc. as solvents, which are used in these commercially available lubricants.
- PAO poly- ⁇ -olefin
- PAG polyalkylene glycol
- graphite and metal soap which are from a completely different technology family, are used as lubricants instead of MoS 2 .
- the present disclosure uses both graphite and metal soap as solid lubricants, and is designed such that these solid lubricants are dispersed in a water-based polymer using water as a solvent.
- these solid lubricants are dispersed in a water-based polymer using water as a solvent.
- the lubricity is further improved.
- metal soaps are often used as additives that are added to oils to increase their viscosity.
- metal soaps are not used as thickeners or thickeners.
- metal soaps are not added to increase the viscosity of oil-based solvents.
- the metal soap has the role of a lubricant and as a means for early drying.
- one of the features of the present disclosure is that a water-repellent metal soap is used after being dispersed in a water-based solvent.
- the basic configuration of the present disclosure mainly uses water as a solvent, but in addition, a lower alcohol having 3 or less carbon atoms is added to the water as a solvent.
- the mixing ratio is 0.5 or more and 10 or less per 100 parts of the volume of water, and the total volume of water and these additives constitutes 95% or more of the total solvent volume (volume / volume%). Let them do it.
- aqueous ammonia may be added as an additive for a further solvent component.
- the present disclosure defines 28-30% ammonia water as so-called concentrated ammonia water. However, if dilute ammonia water is used, the value should be read as a value that has been discounted according to the concentration.
- the solid lubricant had a composition in which 95% or more of the total solid lubricant component weight was composed of graphite and metal soap. Among all solid lubricant components, one containing graphite in a range of 0.5% or more and 5% or less is used. Also, alkaline soap may not be called a solid lubricant, but it works effectively for lubrication in a broad sense. This alkaline soap is designed to contain 1% or less, including zero.
- the binder resin is a water-soluble or water-dispersible polymer. The binder resin was made into a coating agent composition of a polymer or copolymer containing 90% or more of monomers belonging to acrylates and methacrylates when the weight of the total binder resin is taken as the denominator.
- the present disclosure does not include a solid lubricant in an oil-based solvent, as is the case with many commercially available lubricating sprays and pastes.
- the present disclosure has a composition in which a binder resin component and a solid lubricant component are added to an aqueous solvent.
- the water in the chemical volatilizes and evaporates to form a film, which is designed to function as a solid lubricant film.
- the reason for using a water-based solvent is to ensure the safety of workers, to be able to use it even when open flames are prohibited, and to not contain any harmful components.
- the solid lubricant uses graphite and metal soap instead of MoS2 . Both graphite and metal soap are used as lubricants. Graphite and metal soap work together to achieve good lubrication. These combinations give good results and are effective for lubrication even when the screws are engaged with each other, as shown in FIG. 4(b). In the situation where the pin is set at a slight angle (see Figure 5), which often occurs when tightening full-length pin screws, lubrication is required until the pin screw settles into a stable position (Step 1 in Figure 3 (a)). (equivalent to) also works effectively.
- an alkaline soap component is also mixed in to improve lubrication.
- Alkaline soap components are so-called "soaps" that dissolve in water and increase the viscosity of the solvent.
- the alkaline soap component refers to those in a solid state, including those that are incorporated into the film when dry or adhere to the surface of the solid lubricating film.
- the alkaline soap component has the following two roles. That is, the dry alkaline soap itself improves the lubricity, and on the other hand, the alkaline soap in wet conditions melts and becomes slimy, which plays a role in improving the lubricity.
- the binder resin Since water is a solvent, a water-soluble or water-dispersible polymer is used as the binder resin. At this time, the polymer was a polymer or copolymer containing 90% or more of the total binder resin weight using monomers belonging to acrylates and methacrylates.
- the present disclosure utilizes the volatility of lower alcohols and, if possible, the volatility of ammonia, in order to solve the difficulty of drying drugs and ensure early drying properties. This increases the volatilization and evaporation of water. Further, as a suitable range for promoting early drying properties, the size of the solid lubricant was specified so that the average particle size of both the metal soap and the graphite was 5 ⁇ m or less. Furthermore, the present disclosure optimizes the amounts of metal soap and graphite added to achieve early drying. The idea behind reducing the particle size of solid lubricants is to incorporate something that increases the surface area in order to accelerate the early drying of coating chemicals that have not yet dried. Furthermore, micro-sized solid lubricants are effective for lubrication.
- the particle size of the solid lubricant is preferably 5 ⁇ m or less, and the smaller the particle size, the better. Desirably, the particle size of both the metal soap and graphite is 1 ⁇ m or less.
- the mixing regulations for the weight of a water-soluble or water-dispersible polymer corresponding to a binder resin, a solid lubricant, and a water-based solvent are set at a lower limit of 30%, respectively, with respect to the weight of all constituent components. Above, 10% or more, 40% or more. Further, the respective upper limit values are preferably 40% or less, 20% or less, and 50% or less. The reason why this suitable range is set is as follows. Situations where the drug is thinner, ie, more solvent, are acceptable, but result in lower viscosity, lower viscosity, and higher flowability of the drug.
- the weight ratio of the binder resin to the solid lubricant should be between 0.25 and 0.66. It is important to. More preferably, the weight ratio is in the range of 0.3 or more and 0.5. This ratio results in a solid lubricant film being formed on the screw surface. There is a limit to the improvement of lubrication in uniformly dispersing a solid lubricant in a binder resin. If there is too much solid lubricant, it will not completely enter the film and will simply adhere to the surface, which will be detrimental to maintaining improved lubrication. Therefore, the upper limit of the preferred range is 0.5. On the other hand, if the amount is too low, the amount of solid lubricant required for lubrication will be insufficient, making it impossible to maintain the target level of lubrication. Therefore, a preferable lower limit is 0.3.
- a lower alcohol having 3 or less carbon atoms was further added as an additive to take measures to increase volatility in the solvent.
- ammonia water was added depending on the situation. The total volume of these additives was set to 0.5 or more and 10 or less per 100 volumes of water. The former lower alcohol is preferably added in an amount of 0.5 or more and 5 or less per 100 volumes of water.
- Ammonia water is allowed to be mixed in the range of 0 or more and 5 or less per 100 volumes of water.
- Aqueous ammonia may also be intended to be used for pH adjustment. However, it is also intended to dry chemicals by utilizing the volatility of ammonia.
- the ammonia water referred to here is 28-30% ammonia water, so-called concentrated ammonia water. When using dilute ammonia water, the value shall be read as a discounted value according to the concentration.
- the blending ratio of metal soap with a particle size of 5 ⁇ m or less and graphite was such that the weight ratio of graphite was 0.5% or more and 5% or less based on the weight of the total solid lubricant.
- Other solid lubricant-based additives of less than 5% are allowed, but the formulation is such that the remaining major constituent other than the metal soap is primarily graphite.
- Metal soaps work well for lubrication. However, if metal soap is intended to be used in an environment where fire is strictly prohibited, there are limits to the pre-dissolution of metal soap using alcohol. The amount of metal soap added is limited because the metal soap is homogeneously mixed with a coating agent made of a water-based polymer. Therefore, the upper limit of 5% is determined. The lower limit of 0.5% or more was determined because it is a necessary amount to achieve early drying due to the synergistic effect with fine graphite, and was specified in order to simultaneously achieve lubricating properties.
- graphite when used as a lubricant, it has traditionally been mixed and dispersed by adding appropriate additives to a solvent such as a water-based soluble or oil. .
- a solvent such as a water-based soluble or oil.
- graphite is insoluble in water, so in order to design a drug by homogeneously dispersing it in a water-based solvent, it is necessary to create a homogeneous dispersion similar to that used for metal soaps, as shown below. be.
- the premise is that metal soap and graphite are homogeneously mixed in the coating agent.
- metal soaps are said to be water repellent and insoluble in water, although they are soluble in oil. For this reason, metal soaps cannot normally be successfully clouded in the water-based solvent of the present disclosure.
- graphite is also insoluble in water in principle.
- additives are mixed and dispersed in a solvent such as oil or soluble. If you simply dissolve graphite in an aqueous solvent, the graphite tends to float on the surface. It is preferable to disperse graphite as much as possible in order to utilize graphite as a solid lubricant.
- metal soaps which are considered insoluble in water, are mixed with water, which is a solvent for water-soluble or water-dispersible polymers (water-based polymers), and a solvent auxiliary component that is added to the solvent.
- water which is a solvent for water-soluble or water-dispersible polymers (water-based polymers), and a solvent auxiliary component that is added to the solvent.
- metal soap is insoluble in both water and ethanol.
- lower alcohols such as ethanol
- metal soaps are less likely to clump and tend to become fine particles, allowing the metal soaps to remain fine particles. You can also mix metal soap with alcohol and then vigorously stir or apply ultrasonic vibration.
- water alone the metal soaps will aggregate and become large and lumpy, making it impossible to achieve a homogeneous dispersion.
- the metal soap is dispersed although it is in an insoluble state.
- a lower alcohol group such as ethanol
- the metal soap is dispersed although it is in an insoluble state.
- the inventor then came up with the idea that by developing and mixing this with a water-based polymer, it would be possible to create a paint with a homogeneous metal soap dispersion.
- this coating agent is left to stand still, the metal soap will separate as time passes.
- the container containing the chemical was shaken to make it cloudy again before application, it was confirmed that a homogeneous solid lubricant film was formed by evaporating the solvent water, evaporating it, and volatilizing it. Note that when directly dissolved in water, the metal soap tends to form clumps, so there is a high possibility that the solid lubricating film will be non-uniform.
- the metal soap is prepared by dispersing and turbidizing the metal soap in a lower alcohol, and then adding the mixture to water as a solvent. This ensures homogeneous mixing of the metal soap.
- Lower alcohols can be used for graphite in the same way as metal soaps are dissolved in aqueous solvents. However, in a situation where the amount of lower alcohol is less than 10 parts per 100 parts of water as in the present disclosure, it is difficult to dissolve it as much as metal soap. In this case, some of the graphite may be floating on the surface of the solvent, but most of the graphite is dispersed, or it is best to shake the entire chemical before application to ensure it is evenly dispersed. .
- alkaline soap is soluble in water, there is no particular problem in dissolving it in a water-based solvent. In the present disclosure, it may be dissolved with an upper limit of 1%. Dissolution of 1% or more is not good because it increases the viscosity of the entire drug and makes uniform application difficult.
- the present disclosure contemplates a composition that can be used even in a fire-free environment, which is the harshest environment. For this reason, the present disclosure proposes three methods: early drying using lower alcohol, technology to pre-dissolve metal soap and then dissolve it in an aqueous solvent, and safety considerations by adjusting the flash point to a high level. Achieve at the same time.
- the most desirable flash point to aim for here is a state that is evaluated as non-flammable. However, if the flash point of the drug is 60°C or higher, it seems possible to use it in an environment where fire is strictly prohibited at the wellhead. Therefore, utilization of lower alcohols up to that level is acceptable. Note that volatilization of ammonia may also be utilized.
- Ammonia water has a nonflammable flash point, and is also used to adjust the pH of the acrylic binder resin that makes up the coating agent. For this reason, it is preferable to use aqueous ammonia to raise the pH so that it is close to the upper limit of the pH adjustment range, and to take advantage of its volatility.
- the main lubrication agents are metal soap and graphite.
- the components are designed so that the graphite added to improve lubrication does not become integrated with the binder resin during tightening and unfastening, and does not spread over a long period of time to create a tape-like secondary product.
- the inclusion of a trace amount of alkaline soap makes it possible to add further lubrication improvement.
- graphite is restrained along the thread groove.
- the integration of graphite with the binder resin also has an effect, making it easier to form a secondary product in the form of a tape (like a cassette tape).
- a solid lubricant film consisting of metal soap + graphite (plus a small amount of alkaline soap) and binder resin.
- metal soap + graphite plus a small amount of alkaline soap
- binder resin binder resin
- the metal soap component is the main component and the amount of graphite as a subcomponent is limited in the binder resin.
- Graphite is effective in improving lubrication performance.
- graphite can be used in a tape form (such as a cassette tape) when the sliding area is limited, such as in a threaded structure, and the route through which solid lubricants and secondary products move is narrowly limited. A secondary product of state) is formed. This results in an increased tendency for it to become stuck in the thread gaps and induce seizing. Therefore, graphite is prepared with a lower limit of 0.5% or more and an upper limit of 5% or less relative to the total weight of all solid lubricant components including the alkali soap component.
- the lower limit is determined from the required content to take advantage of the lubrication-improving effect of graphite.
- the upper limit of the graphite content is determined because adding too much graphite prevents the formation of a tape-shaped secondary product mainly composed of graphite when tightening and unfastening the screw. This includes cases in which the solid lubricant film structure ranges from situations in which graphite + metal soap are completely incorporated into the film, to cases in which graphite itself is distributed to the extent that it appears to be attached to the outermost surface of the solid lubricant film. .
- the total amount of graphite must be kept at an upper limit of 5% or less based on the total solid lubricant (including alkaline soap content).
- a more suitable range is 1% or more and 3% or less.
- the lower limit is set to 1% or more and the upper limit is set to 3% or less, in this order, the lubrication improvement effect of graphite can be expected to be even greater, and the formation of secondary products with a tape structure is more likely to be avoided.
- those that promote lubrication are metal soap, graphite, and a trace amount of alkaline soap.
- Adding graphite improves the lubricating behavior that is insufficient with metal soap.
- graphite-containing lubricants avoid what often occurs in situations where the slippery part, such as an oil country tubular thread, is confined to a narrow area, such as a thread groove. It is necessary to avoid tape-like secondary products that are formed during tightening and untightening of screws due to the addition of graphite, resulting in seizure.
- the reason why a tape-shaped secondary product derived from graphite becomes difficult to form when the above range is limited is considered to be as follows.
- the lower limit is the value necessary to utilize the lubrication improvement effect of graphite.
- the upper limit is the value necessary to induce the tape-like secondary product to become flaky or powder-like. If it is 5% or less, it can be estimated that even if individual graphite deforms, it is difficult to connect to each other and form a long tape shape, although this is a rule based on experimental results.
- the particle size of graphite is 5 ⁇ m or less. In the tape-shaped secondary product, there are cases where individually elongated graphite is connected to each other during tightening and unfastening, and cases where the size of each graphite is larger than 5 ⁇ m.
- the size of graphite is set to prevent this.
- the thickness of the solid lubricant coating may be approximately 5 ⁇ m in the thin portion. If the size of the graphite is larger than the film thickness in that localized portion, the solid lubricant film itself is likely to be destroyed starting from the interface between the binder resin and the solid lubricant during tightening and unfastening. Therefore, it makes sense to avoid this.
- the reason why the size regulation for metal soap is preferably 5 ⁇ m or less is to prevent the solid lubricant coating itself from becoming easily destroyed, similar to graphite. At the same time, the fine structure of both metal soap and graphite increases the contact area with the solvent, increasing the number of drying points. Therefore, the size of 5 ⁇ m or less also contributes to early drying.
- the solid lubricating film of the present disclosure has a structure in which binder resin, graphite, and alkaline soap are homogeneously contained in the binder resin. However, some parts are composed of metal soap, graphite, and alkaline soap, which are distributed as if attached to the outermost layer. In any case, these solid lubricants are the basis for achieving lubrication of oil country pipe threads.
- Metallic soap is a dry lubricant and functions as a lubricant in its dry form. Furthermore, when the metal soap generates frictional heat due to poor lubrication during tightening and loosening, it functions to semi-melt or melt and form a lubricating film on the parts that require lubrication.
- the present disclosure does not utilize the effect of mixing oil and metal soap to form a grease, which is common in metal soap applications.
- Graphite has a laminated structure in which strong planar structures are weakly bonded by van der Waals forces, and when force (torque) is applied to graphite, the lubrication effect of the planar surfaces slipping is utilized.
- force tilt
- a long tape-shaped secondary product is formed, and if the content is devised and the size is adjusted to a suitable range to prevent seizure, good.
- Alkaline soaps like metal soaps, may also function as dry lubricants within binder resins. At the same time, alkaline soaps rather combine with minute moisture and become slimy. As a result, the effect of the alkaline soap is to make the oil country tubular screws, which are always set slightly obliquely, slip and guide the screws to a stable position. In actual tightening of oil country pipe screws, etc., there are situations where Ranges 2 and 3 (8 m and 12 m, respectively) are set at a slight angle. It is rather normal to use the initial setting position of the oil country pipe screw, such as the reference numeral 1a (10) in Fig. 5 and Fig.
- the pin screw is lightly tightened by hand to maintain engagement to some extent. . Then, it cannot be denied that when the solid lubricant film is removed more than necessary and damaged when it is brought to the position shown in FIG. 4(b) while being tightened with power tongs several times. It can also function effectively to avoid unnecessary scraping of the solid lubricant coating so that the pin screw slides into the normal position of the box screw, and to guide the pin screw to the normal engagement position.
- One of the features of the present disclosure is that the lubrication of the metal soap is improved by adding graphite, and furthermore, fine alkaline soap is contained. The key to this is to smoothly guide, or slide into, the proper engagement position. At this time, depending on the amount of graphite added, it is necessary to take measures to prevent the graphite from forming a tape-like structure along the thread grooves, which may cause seizure.
- the solid lubricant when the solid lubricant dries into a film, all of the solid lubricant is taken into the film, and the solid lubricant is mainly taken into the film but is distributed on the film surface.
- the portion outside the membrane refers to the portion that is weakly attached to the membrane surface or simply rests on the outermost layer.
- Metal soap and graphite have two contributions. That is, there are parts of these solid lubricants that are separated from the film and contribute to lubrication individually and in combination, and parts that contribute to lubrication as secondary products integrated with the binder resin.
- the weight formulation of the binder resin component made of a water-based polymer (acrylic), the solid lubricant, and the water-based solvent is set within a preferable range. I set it as follows. That is, with respect to the weight of all constituent components, the respective lower limits are 30% or more, 10% or more, and 40% or more, and the respective upper limits are 40% or less, 20% or less, and 50% or less.
- the weight ratio of the graphite to the total amount of solid lubricant is 0.5% or more and 5% or less of the total solid lubricant.
- the reason why the lower limit is set to 0.5% is to maintain high lubrication without producing tape-like secondary products, as described above. Also, at this level, it can be mixed homogeneously into a water-based solvent.
- the upper limit of 5% or less is intended to avoid harmful effects caused by too much graphite. If it exceeds this, in addition to the lubrication point of view, the graphite will not dissolve well in the aqueous solvent. In this case, there is a high risk that the graphite will form lumps due to the association of graphites with each other. In addition, it may not be possible to properly mix the compound into an aqueous solvent. Alkaline soap also needs to be mixed in at an upper limit of 1%. The reason for this is to facilitate guiding the screws to the proper engagement position.
- the chemical of the present disclosure is applied to repair mild seizures caused by screw seizure.
- the solid lubricant coating may be missing, a portion of the solid lubricant coating may be missing, or the metal of the threaded portion may be shaved off.
- the thickness is on the order of 1 to 2 mm.
- the formulation regulations for the weight of water-based polymer (acrylic), solid lubricant, and water are completely changed.
- the following lower limits were set for the weights of the constituent components. That is, the respective lower limits were set to 30% or more, 10% or more, and 40% or more. Further, the respective upper limit values were set to 40% or less, 20% or less, and 50% or less.
- the solid lubricant is composed mainly of metal soap with graphite and alkali soap added, and the binder resin is a water-soluble or water-dispersible binder resin that dissolves in a water-based solvent. It is best to apply the drug mainly to the scraped area, and also apply a thin layer of the medicine to other areas as well.
- the burnt-in area is physically embedded with paint. Once tightened and untightened, the filled part will appear to be pressed down from above. As a result, the area that has been scraped and cured will eventually be filled in with this drug.
- the viscosity of the coating agent is adjusted to 1000 mPa ⁇ sec or less, it is possible to ensure a state of high fluidity so that it can penetrate into the defective area.
- the viscosity is achieved by increasing the composition of the aqueous solvent.
- the viscosity is higher than that, it becomes difficult to achieve the purpose of assisting lubrication or repairing mildly burned areas. Therefore, the above concentration range is adjusted in consideration of this point.
- the solid lubricant film and coating agent of the present disclosure were evaluated for suitability using an evaluation method suitable for the environment used in an actual well, and the upper and lower limits of the parameters were defined. This makes it possible to provide lubrication assistance or repair mildly burned areas that can withstand use in actual wells.
- evaluation using weight tongs is an evaluation method invented by the inventor.
- This evaluation method can be evaluated by applying the severe self-weight of a full-length pin in an actual well, and by setting it in an unbalanced state, including the effects of damage to the solid lubricant coating. This evaluation provides confidence in the parameters of this disclosure.
- the evaluation method is to attach a weight of one to three actual length pins to the upper end of the short pin. Further, the initial setting position of the screw is such that about half of the pin thread is exposed to the box screw.
- a coating agent that does not use MoS 2 , is environmentally friendly, and can withstand use in actual wells as a coating agent for repairing oil country pipe threads and improving lubrication. .
- FIG. 1 It is a figure showing an oil country pipe and a threaded joint of an oil country pipe. They are a diagram (a) of a tightening chart in a conventional laboratory test and a diagram (b) showing an initial set position at that time. They are a diagram (a) of a tightening chart in an actual well, and a diagram (b) showing the initial set position at that time. It is a diagram simulating the tightened state of an oil country pipe threaded joint. It is a schematic diagram which illustrates the state of a set of a pin screw and a box screw (description of a screw thread etc. is abbreviate
- weight tongs are a diagram illustrating the conditions of a new laboratory test (descriptions of screw threads, etc. are omitted). It is a figure showing an example of installation of a weight under new laboratory test conditions (weight tongs). In FIG. 7, descriptions of threads and the like are omitted.
- the chemical of this embodiment is a chemical for imparting lubricating performance to the metal surface of metal parts such as oil country tubular goods.
- the main components of the drug are a solid lubricant, a binder resin, and a solvent component.
- the main component refers to, for example, a material in which the remainder is unavoidable, or a solid lubricant, binder resin, and solvent component that accounts for 95% or more of the total weight.
- the solvent component has water as its main component, and a lower alcohol having 3 or less carbon atoms is added to the water as an additive.
- the volume of the additive to water is 10 or less per 100 of the volume of water. More than 95% of the volume of the solvent is composed of the water and the additives.
- Aqueous ammonia may be further added as the above additive. It is preferable that the solvent accounts for, for example, 40% or more and 50% or less of the total weight of the drug.
- the solvent includes, for example, a lower alcohol having three or less carbon atoms and aqueous ammonia, to which at least a lower alcohol having three or less carbon atoms is added.
- the volume of the lower alcohol having 3 or less carbon atoms is 0.5 or more and 10 or less per 100 volumes of water constituting the solvent.
- the volume of ammonia water is 0 or more and 5 or less per 100 volumes of water constituting the solvent.
- Examples of lower alcohols having 3 or less carbon atoms include lower alcohols selected from one or more of methanol, ethanol, isopropyl alcohol, normal propyl alcohol, and industrial ethanol.
- Solid lubricant Contains graphite and metal soap as solid lubricants.
- the graphite and metal soap account for more than 95% of the total solid lubricant component weight.
- the solid lubricant preferably accounts for, for example, 10% or more and 20% or less of the total weight of the drug.
- the main component of solid lubricants is metal soap. That is, the metal soap is contained in a larger amount than the graphite in terms of weight ratio.
- Graphite is contained in an amount of, for example, 0.5% or more and 5% or less of the total solid lubricant in terms of weight ratio.
- a more preferable range is 1% or more and 3% or less. When the lower limit is set to 1% or more and the upper limit is set to 3% or less, the lubrication improvement effect of graphite can be expected to be even greater, and the formation of tape-structured secondary products is more likely to be avoided.
- alkaline soap is added in an amount of 1% or less, including zero. Aims to achieve lubricating behavior similar to metal soap and graphite. In addition, alkaline soap also effectively functions to slide the pin screw and box screw into the proper engagement position. Moreover, as a suitable range, the particle diameters of both the metal soap and the graphite are preferably 5 ⁇ m or less, for example. The reason for this is, as already mentioned, to prevent the solid lubricant film from being easily damaged during tightening and unfastening, and to help dry it out quickly by making it fine in size.
- the former consists of one or more types of soaps, each of which is a compound (metallic soap) consisting of a fatty acid from Group A and a metal element (metal ion) from Group B.
- the latter consists of a compound (alkaline soap) consisting of the following group A fatty acid and group C metal element (metal ion).
- Group A stearic acid, behenic acid, lauric acid, 12-hydroxystearic acid, oleic acid, montanic acid
- Group B Mg, Ca, Zn, Ba
- Group C Na, K
- the binder resin is a water-soluble or water-dispersible polymer.
- the polymer is a polymer or copolymer containing monomers belonging to acrylates and methacrylates in an amount of 90% or more by weight of the total binder resin.
- the binder resin accounts for, for example, 30% or more and 40% or less of the total weight of the drug.
- the water-soluble or water-dispersible polymer constituting the binder resin is, for example, a polymer composed of a single monomer among the monomers described in (1) to (4), or a copolymer composed of two or more monomers. be.
- the chemical is prepared by dispersing metal soap in lower alcohol to make it turbid, and then adding it to water as a solvent.
- ⁇ Oil country pipe repair method> This is an oil country tubular repair method that repairs the lubricant film on the threaded portion of oil country tubular goods. After curing the area where seizing has occurred among the threaded portions of the oil country tubular goods, the coating agent of the present disclosure is applied to at least the curing portion. This allows the chipped area to be repaired by filling it with a film containing graphite.
- the coating agent of the present disclosure is applied onto the existing lubricating film formed on the oil country pipe formed on the threaded portion. This aims to improve the lubrication performance.
- the oil country tubular goods are, as shown in FIG. 1, a box 2 having a female thread 2a and a pin 1 having a male thread 1a.
- the oil country pipe threaded joint consists of a box 2, such as a coupling, having a female thread 2a, and a pin 1 having a male thread 1a.
- a lubricating coating including the solid lubricating coating of the present disclosure is formed on the contact surface (fastening surface 10) of the threaded portion of at least one of the box 2 and the pin 1.
- a lubricating coating having a solid lubricating coating is formed on the threaded portion of the oil country tubular goods of this embodiment.
- the solid lubricant coating includes a binder resin and a solid lubricant dispersed in the binder resin.
- a solid lubricant film has a solid lubricant dispersed in a binder resin as a matrix component.
- the solid lubricant contains graphite and metal soap, and the graphite and metal soap account for 95% or more of the total solid lubricant component weight.
- the particle size of the graphite is, for example, 5 ⁇ m or less
- the particle size of the metal soap is, for example, 5 ⁇ m or less.
- the amount of metal soap is 0.5% or more and 5% or less of the total solid lubricant in terms of weight ratio.
- the metal soap is, for example, one or more types of metal soaps, each of which is a compound consisting of a fatty acid selected from Group A and a metal element (metal ion) selected from Group B.
- the alkaline soap consists of one or more types of alkaline soaps, for example, consisting of a compound consisting of a fatty acid selected from the following group A and a metal element (metal ion) selected from the following group C.
- Group A stearic acid, behenic acid, lauric acid, 12-hydroxystearic acid, oleic acid, montanic acid
- Group B Mg, Ca, Zn, Ba
- Group C Na, K
- the binder resin is a water-soluble or water-dispersible polymer, and the polymer is a polymer or copolymer containing 90% or more of monomers belonging to acrylates and methacrylates when the weight of the total binder resin is taken as the denominator.
- the water-soluble or water-dispersible polymer constituting the binder resin is a polymer composed of a single monomer among the monomers described in (1) to (4), or a copolymer composed of two or more monomers.
- the solid lubricating coating has a thickness of 10 ⁇ m or more and 100 ⁇ m or less, and is soft with a pencil hardness of B or less.
- this film thickness refers to the so-called crest part (corresponding to the thread thread) on the surface of the thread part, which can be measured non-destructively using ultrasound or other means.
- OCTG refers to the crest (flat part) of the thread, which is often found in premium joints, such as the inverted hook type for box screws and the hook type for pin screws. It is not the film thickness of the stabbing flank or loading flank where the threads stand vertically.
- a base film (not shown), such as a Mn phosphate chemical conversion treatment film, an electroplated film, etc., may be provided below the solid lubricant film.
- At least one of the box and the above-mentioned pin is made of an oil country country pipe on which the lubricating coating of the present disclosure is formed.
- a coating having a harder hardness than the solid lubricating coating is formed on the threaded portion of the other OCTG.
- the drug of the present disclosure has a main component system in which a water-soluble or water-dispersible polymer (aqueous polymer) is used as a binder resin, a solid lubricant is a mixed system of metal soap and graphite, and water is used as a solvent.
- a coating agent composed of coating agents.
- the drug of the present disclosure is utilized as a solid lubricant coating for oil country tubular threads.
- the agent of the present disclosure can also be used when lubricity that is one level higher than the solid lubricant coating that has already been formed is required. It is also possible to apply the agent of the present disclosure onto an existing solid lubricant coating for the purpose of improving lubricity or preventing seizure, including in a preventive sense. Further, it is used, for example, when a slight seizure occurs only in the thread part of a screw consisting of a thread part and a seal part. That is, when performing touch-up partial repairs at the wellhead, the chemical of the present disclosure is applied to the surface to be repaired after curing. This constitutes the oil country tubular goods and oil country tubular threaded joints of the present disclosure.
- Lubrication assistance refers to applying the agent of the present disclosure to the entire surface of the solid lubricant coating already provided on the threaded portion to improve lubricity. In most cases, the goal is to increase the number of times of tightening and unfastening by two to three times, but lubrication assistance is considered good (passed) if the number of times of tightening and unfastening can be increased by at least one time.
- the burned-in parts are limited to the burned-in parts of the screw threads, and the burned-in parts of the seal parts are excluded. Repairs are carried out to re-establish lubrication after curing the burned-in area using a grinder, file, paper, etc. Specifically, the agent of the present disclosure is applied only around the burned-in area or over the entire surface. If the tightening can be increased one or more times from the seize state, it is considered good (passed). Furthermore, if it can be tightened and untightened one or more times (two or more times in total), it is considered to be even better.
- the present disclosure employs an aqueous solvent, it is intended to quickly dry the applied drug by the following.
- the method of incorporating the solid lubricant into the binder resin is changed.
- the level of premature drying is determined based on two criteria. The first criterion is whether or not it is possible to achieve faster drying compared to when the above measures are not taken. In the case of leaving in the air, the comparison is made between leaving in the air, and in the case of air drying, when comparing the air drying, the goal is to dry quickly. Evaluate the places and positions to be compared using equivalent positions.
- the second criterion is whether or not the material can be dried by blowing air (without heating) within 5 minutes, more preferably within 1 minute.
- the goal is to be able to dry within 30 minutes, preferably within 15 minutes, and more preferably within 5 minutes. Dry here means a semi-hardened level or a hardened dry level beyond a touch-dry level.
- the paint terms dry to the touch and semi-dry are defined in accordance with JIS K5500-2000. However, in the present disclosure, blowing air in an atmospheric environment without heating is based on the results confirmed in an environment of 14-18°C.
- the coating amount is 0.1 g/mm 2 or less on a metal surface
- it is preferable that the coating has suitable early drying properties such that it can dry within 30 minutes at room temperature when left to dry in the air.
- This early drying property is at a level that can be achieved by the parameters defined in this disclosure, including the detailed description below. If this can be done, it will be possible to dry more quickly using blow drying or warm air drying.
- the present disclosure uses a coating agent formulated to have low viscosity and fast flow. These evaluation positions are based on the fact that when a water-based paint based on a water-based acrylic binder resin is applied to an oil country pipe screw lying on its side, the liquid tends to drip along the thread groove and accumulate at the 6 o'clock position. be. For this reason, drying in that area tends to be a little slower, so the comparison evaluation will be made between the 9 o'clock and 3 o'clock positions.
- any dripping will fall to the ground, so there is no place for it to collect.
- water droplets may form at the tip of the pin. In that case, exclude that part and evaluate the drying time. In the case of a box screw, it also hangs downward.
- there is a non-zero tendency for buildup to build up at the shoulder level difference so we will exclude that area when discussing drying time.
- the cured area where the burn has actually occurred has physical depressions, etc., and the agent of the present disclosure is also applied to fill those areas. Therefore, it is only necessary to discuss the dry state of the surface. Among the areas mentioned above, drying time will be evaluated at areas where there are no problems, and early drying performance will be discussed. The reason for the need for early drying is that this coating agent and the solid lubricant film made using it are expected to be used for touch-up repair work at the wellhead, where the most severe conditions are minor seizures and other problems. This is because they are doing so. Therefore, it is intended that the problem areas be repaired by scraping them with a file, abrasive paper, etc., and then repaired using the coating agent of the present disclosure.
- Coating chemical repair refers to filling the repaired area and ensuring lubrication. For this reason, we intended to dry the product quickly by leaving it to dry in the atmosphere or by blowing air, assuming that it could be used with no open flames or that utilities related to drying could not be used.
- the present disclosure uses an aqueous solvent to achieve early drying through the following measures. In other words, the volatility of lower alcohols and ammonia is utilized. In addition, we will set the blending range and manage the size of metal soap and graphite. Furthermore, we will take measures to prevent the metal soap and graphite from clumping together, and change the method of incorporating the solid lubricant into the binder resin. Use these to dry quickly. The details will be explained for each individual item below, but the overall overview will be about the design concept of the coating agent.
- the agents of the present disclosure include lower alcohols.
- the concentration is adjusted so that the flash point of the drug is 60°C or higher, or it can be considered non-flammable, as it is intended to be used in environments where open flames are strictly prohibited.
- the volatility of lower alcohols is then utilized to achieve early drying.
- the drug of the present disclosure does not use thinner-based VOCs. This is to comply with the strict prohibition of open flames at the wellhead, to ensure the health and safety of workers, and to allow work to be carried out while avoiding the installation of exhaust equipment such as drafts.
- the volatility of aqueous ammonia can also be used to control the concentration of these chemicals within an appropriate range at a level that allows them to be used without using draft equipment.
- early drying is achieved by controlling the concentration and particle size of the metal soap and graphite contained within appropriate ranges. Specifically, a size with a small average particle size is selected, and the concentration is adjusted to an appropriate amount. This increases the total surface area of the solid lubricant and utilizes the volatilization of lower alcohol and ammonia to form a film at an early stage.
- the size (average particle size) of both the metal soap and graphite used is 5 ⁇ m or less, preferably 1 ⁇ m or less. This increases the surface area of the solid lubricant and enhances drying. At the same time, it is possible to reduce damage to the solid lubricant film, which tends to break at the interface between the binder resin, metal soap, and graphite during tightening and unfastening. If the thickness exceeds 5 ⁇ m, the solid lubricant film may be distributed through the film in vertical wall portions where the solid lubricant film tends to be thin, making it easy to break.
- the vertical wall portion is, for example, a stabbing flank or a loading flank.
- metal soap and graphite are first dissolved in lower alcohol and then mixed into a water-based solvent or water-based polymer mixture.
- Metallic soaps also serve as the main ingredient in lubricants.
- graphite works to support the lubricant and also fills in the dents formed in the repaired surface during touch-up repairs.
- the viscosity of the coating agent is adjusted so as not to be applied too thickly. In short, it is intended to have a low viscosity and smooth liquid viscosity as a drug. Although the lower limit of the viscosity is not set, it is approximately 40 mPa ⁇ sec or more.
- the viscosity When a water-soluble or water-dispersible polymer material is added to an aqueous solvent, the viscosity will not be 1 mPa ⁇ sec, which is the viscosity of water, and the viscosity will be high. As a result, the level is approximately 40 mPa ⁇ sec or higher.
- the chemical mainly consists of a solid lubricant, a binder resin, and a solvent that does not remain in the coating after the chemical is applied.
- the solvent is mainly water.
- One or more kinds of lower alcohols having 3 or less carbon atoms were further added to the water as an additive.
- aqueous ammonia may also be added as the above additive.
- the amount of the additive is 10 or less per 100 by volume of water. Further, the total volume of water and the above-mentioned additives is 95% (vol/vol%) or more of the total solvent volume.
- the main components of the solid lubricant are graphite and metal soap.
- the main components mean that the total weight of graphite and metal soap is 95% or more of the total weight of the solid lubricant components.
- the binder resin is mainly composed of a water-soluble or water-dispersible polymer. In the polymer, a polymer or copolymer composed of monomers belonging to acrylates and methacrylates accounts for 90% or more of the weight of the total binder resin component.
- the present disclosure mainly consists of a water-based solvent, a solid lubricant mainly composed of graphite and metal soap, and a polymer and its copolymer composed of monomers belonging to acrylates and methacrylates. Consists of binder resin. In each case, the term "subject" refers to 95% or more, 95% or more, and 90% or more of each component. The point is that a slight amount of impurity, unavoidable mixture, or nasal spray is acceptable.
- the stability of the film formed by applying the drug will decrease, and there is a possibility that the properties expected by the present disclosure may not be achieved.
- the solvent including alcohol, ammonia, etc.
- Polymers composed of monomers belonging to the acrylate and methacrylate classes form a dry film (matrix) by themselves.
- the film is a film that homogeneously holds a solid lubricant of metal soap and graphite in the film (matrix). A portion of the solid lubricant may be attached to the surface layer of the film (matrix), or may be partially embedded in the film (matrix) and partially exposed to the surface.
- lower alcohol and ammonia are used to homogeneously dissolve the metal soap and to quickly dry the film by utilizing their volatility. This will be explained in detail again below.
- the blending ratios of binder resin, solid lubricant, and water are as follows: binder resin (water-soluble or water-dispersible polymer), solid lubricant (metallic soap and graphite), and water-based solvent as a solvent, respectively.
- binder resin water-soluble or water-dispersible polymer
- solid lubricant metallic soap and graphite
- water-based solvent as a solvent
- the following value is preferable as the lower limit. That is, preferably 30% or more, 10% or more, and 40% or more, respectively.
- the coating agent is mixed so that the total amount of these agents is 100%. Water has no environmental problems. For this reason, water is selected as the main component of the solvent.
- the present disclosure uses solid lubricants in the amounts and sizes listed below, as well as volatile but less problematic lower alcohols and aqueous ammonia.
- the drug can be applied in a thin layer.
- it is preferable to add 40% or more of water as described above.
- the water content is sufficient to contain the required amount of water-soluble or water-dispersible polymer.
- the reason why we set the upper limit of water to 50% or less is because if it exceeds that, the binder resin itself will become too thin, and the viscosity will become too low, making it impossible to apply the required amount of the chemical. It is stipulated.
- the water-soluble or water-dispersible polymer refers to a polymer mainly composed of water-based acrylic (methacrylic) resin. It is preferable to mix this to 30% or more and 40% or less.
- This range is specified in order to ensure early drying by keeping the viscosity within an appropriate range, to mix the solid lubricant into the binder resin film and retain it, and to place the solid lubricant alone on the surface of the solid lubricant film. This is to position it so that it also adheres to the surface. If it is less than 30%, the liquid viscosity of the drug will be too low, resulting in high fluidity and the solid lubricating film will become thin, making it impossible to maintain the lubricating properties of the film. If it exceeds 40%, the viscosity of the drug will increase, and depending on how it is applied, the film will locally become thicker, increasing the possibility that early drying properties will not be achieved.
- Solid lubricants are mainly composed of metal soap and graphite, and the main component is metal soap. That is, the metal soap is contained in a larger amount than the graphite.
- the reason why the content of the solid lubricant is set as a preferable range of 10% or more and 20% or less is that this is also an appropriate range set to satisfy multiple factors at the same time.
- the reason why it is set at 10% or more is that the desired lubrication cannot be achieved unless more solid lubricant is added than necessary. At the same time, this is to ensure the surface area and amount of the solid lubricant, which will be described later, and to expect the effect of promoting early drying. Further, the reason why the content is set to 20% or less is to avoid the negative effects caused by an excessive amount of graphite.
- the weight ratio of the binder resin and the solid lubricant should be the same as the weight ratio of the solid lubricant to the weight of the binder resin, assuming that it can be dissolved in the water-based solvent mentioned above. However, it is important to formulate it so that it is between 0.25 and 0.66. More preferably, the weight ratio is in the range of 0.3 or more and 0.5. This ratio results in a solid lubricant film being formed on the screw surface.
- lower alcohol As a solvent component other than water, one or more types of lower alcohols having 3 or less carbon atoms are added in an amount of 0.5 to 10 per 100 volumes of water. Furthermore, ammonia water can be added in an amount of 0 or more and 5 or less per 100 volumes of water.
- the lower alcohol having 3 or less carbon atoms is preferably one or more lower alcohols selected from methanol, ethanol, isopropyl alcohol, normal propyl alcohol, and industrial ethanol.
- Lower alcohols are one means for promoting early drying. It is assumed that the chemical agent of the present disclosure will be used for touch-up repairs at the wellhead. Therefore, under the most severe conditions, chemicals must be usable even when exposed to open flames. Furthermore, in consideration of the safety and health of workers, it is preferable not to use thinner-based organic solvents such as toluene, xylene, and benzene, and to ensure that the flash point of the chemical does not become low. For this purpose, a lower alcohol having 3 or less carbon atoms is used. As detailed below, in order for the flash point of the drug to be 60°C or higher, or for it to be non-flammable, it is necessary to limit the upper limit of the concentration of these lower alcohols and adjust the flash point of the drug to be high. be.
- lower alcohols have a flash point of 10 to 15°C and a boiling point of about 65 to 100°C when the composition is 100%. Therefore, it is necessary to mix the lower alcohol with water as a solvent, binder resin, and solid lubricant so that the chemical has an appropriate flash point. Also, it is dangerous to mix a large amount of lower alcohol to promote early drying of the drug in an environment where fire is strictly prohibited.
- the lower limit (0.5 or more per 100 volumes of water) means the minimum that can utilize volatility.
- the upper limit (10 or less per 100 volumes of water) is set as an allowable upper limit for flash point adjustment.
- Ammonia water may be added to adjust the pH to a level at which the water-based polymer can stably exist. For this reason, it is also possible to add ammonia water so that the pH range is at the upper limit of the pH range specified by each water-based polymer, and further utilize the volatilization of the ammonia.
- the reason why the upper limit of addition of ammonia water is set to 5 or less per 100 volumes of water is as follows. In other words, this upper limit value is set because realistically only about 5 or less additions are required. Usually, the upper limit is 1 to 2 per 100 volumes of water.
- ammonia water is expressed as concentrated ammonia water (containing 28-30% ammonia). When using diluted ammonia, it shall be interpreted as a rebate specified in the blending ratio of concentrated ammonia water.
- the lower alcohol having 3 or less carbon atoms refers to methanol, ethanol, isopropyl alcohol, normal propyl alcohol, and industrial ethanol.
- the reason why alcohols with carbon atoms of 4 or more were not targeted is that their solid solubility with water is slightly reduced.
- the lower alcohol has the role of blending the solid lubricant metal soap without clumping it up and preventing it from associating with the metal soap at the same size as when it is added.
- metal soap If metal soap is simply dissolved in water, due to its water-repellent properties, the metal soaps will not mix with the water and will combine with each other to form clumps. Even if you try to mix metal soap particles with a particle size that is less than the specified value into medicine, if you mix the metal soap directly into water, it will not disperse sufficiently. Therefore, even in the form of a film, the metal soap is not evenly incorporated into the binder resin, resulting in a film that is uneven, which is not good for lubrication. For this reason, a method should be adopted in which a mixture of lower alcohol and metal soap is mixed with a dispersion of a water-soluble or water-dispersible polymer and water. At this time, it is necessary to adjust the concentration of lower alcohol and the content of metal soap so that they fall within the range prescribed by the present disclosure.
- the average particle size of graphite is 5 ⁇ m or less, and the average particle size of metal soap is 5 ⁇ m or less. Further, in the solid lubricant, the weight ratio of graphite is 0.5% or more and 5% or less, and the remaining main component is metal soap.
- alkaline soap can be contained with an upper limit of 1%. In the present disclosure, lubrication is mainly provided by metal soap and further improved by graphite. Alkaline soap can also be expected to improve lubrication.
- the additional benefits of alkaline soap include the following functions: That is, the alkaline soap effectively functions to induce the pin screw and box screw to slide from the initial misaligned position to the normal position. Alkaline soaps are effective, especially in slightly damp conditions. In addition, alkaline soap has the effect of effectively causing the threads to slide into the proper engagement position even when the threads are wet due to rain or backflow from a well.
- the size of the solid lubricant is one means for promoting early drying.
- metal soap and graphite which are solid lubricants that are insoluble in water, can be used by reducing the particle size to increase the surface area that comes in contact with the solvent, and by taking advantage of the volatility of lower alcohols and ammonia. , achieves early drying.
- the size is 1 ⁇ m or less. If the thickness exceeds 5 ⁇ m, the solid lubricant will come out at the same level as the thickness of the solid lubricant film.
- the thickness needs to be 5 ⁇ m or less.
- the film thickness is defined as a preferable range of 10 ⁇ m or more and 100 ⁇ m or less. If the particle size of the graphite and metal soap is 5 ⁇ m or less, preferably 1 ⁇ m or less, the fear that the membrane will be easily destroyed when tightening and loosening the oil country pipe screw can be reduced.
- solid lubricants are mainly composed of graphite and metal soap. However, if it is less than 5%, it may be mixed in as a solid lubricant and as an impurity.
- BN boron nitride
- mica mica
- talc talc
- MCA melamine cyanurate
- PTFE polytetrafluoroethylene
- alkali soap groups if in trace amounts, will interfere with the effects of the invention intended by the present disclosure. do not.
- tape-like secondary products are more likely to form during tightening and untightening with the addition of graphite.
- the origin of the tape-like secondary product is a structure formed mainly of graphite extending along the thread groove. If a tape-shaped secondary product of graphite is formed for a long time so as to cancel out the lubrication improvement effect of the addition of graphite, and if it becomes clogged somewhere in the thread gap, there is a high risk of seizure occurring. Due to the graphite being dispersed in the binder resin, there is an undeniable tendency to create structurally tape-like secondary products. However, burn-in can be avoided by changing the tape shape into a peeled piece, a fragment, or a powder.
- the graphite concentration of the present disclosure needs to be 0.5% or more and 5% or less based on the total solid lubricant weight.
- the lower limit is the value necessary to utilize the lubrication improvement effect of graphite.
- the upper limit is the value necessary to induce the tape-like secondary product to become flaky or powder-like. If it is 5% or less, this is a rule based on experimental results, but it can be assumed that even if individual graphite deforms, it is difficult to connect with each other and form a long tape shape. If it exceeds 5%, there is a risk that the amount of tape-shaped secondary products derived from the solid lubricant in the binder resin and graphite in the form of adhering to the surface without being incorporated into the binder resin will be too large. be.
- a tape-shaped secondary product made only of graphite may be produced, and as a result, a strong tape-shaped secondary product may be produced. Then, when tightening and unfastening, the screw gets stuck in the screw gap, which inevitably causes seizure.
- the size of graphite is 5 ⁇ m or less.
- the tape-shaped secondary product has the following tendency when individually stretched graphite is connected to each other during tightening and unfastening, and when the size of the individual graphite is larger than 5 ⁇ m. In other words, there is a high tendency for the elongated form of large graphite to form a long tape structure. This is to prevent this by setting the thickness to 5 ⁇ m or less. In addition, when considering the solid lubricant film, it cannot be denied that the thickness of the solid lubricant film may be approximately 5 ⁇ m in the thin portion.
- the size of the graphite is larger than the film thickness in a localized area, the solid lubricant film itself is likely to be destroyed starting from the interface between the binder resin and the solid lubricant during tightening and unfastening. . Furthermore, by setting the thickness to 5 ⁇ m or less, it is possible to avoid this problem. Further, the reason why the size regulation for metal soap is preferably 5 ⁇ m or less is to avoid the solid lubricant coating itself from becoming easily destroyed, similar to graphite. At the same time, both metal soap and graphite have fine structures, which increases the contact area with the solvent and increases the number of drying points. Therefore, the thickness of 5 ⁇ m or less also contributes to early drying.
- the present disclosure includes the case where there is a portion where either metal soap or graphite contributes to lubrication singly or in combination, and a solid lubricant distributed as if on a film. Adjustment is made so that the concentration distribution as described above and the suitable size are obtained so as not to create a tape-shaped secondary product mainly composed of graphite.
- the mixing regulations for the water-based polymer (acrylic) binder resin, solid lubricant, and water should be set at a lower limit of 30% by weight relative to the weight of all constituent components. % or more, 10% or more, and 40% or more. Further, the respective upper limit values were set to 40% or less, 20% or less, and 50% or less.
- the amount of solid lubricant is 10% or more and 20% or less of the total weight of the drug.
- Most of the solid lubricant is metal soap rather than graphite, and the amount of graphite is adjusted to be equal to 0.5% or more and 5% or less of the weight of the total solid lubricant (including alkali soap). .
- the lower limit is set to 0.5% in order to maintain high lubrication without producing tape-like secondary products, as described above. Also, at this level, it can be homogeneously mixed with water as a solvent.
- the upper limit of 5% or less is intended to avoid harmful effects caused by too much graphite. If this is exceeded, there is a high risk that the graphite will form lumps due to the association of graphites with each other, that it will not be able to mix well with an aqueous solvent, or that the generation of tape-like secondary products will become significant.
- the water-soluble or water-dispersible polymer constituting the binder resin is preferably a polymer composed of a single monomer of the following (1) to (4) or a copolymer composed of two or more monomers.
- binder resin a water-soluble or water-dispersible polymer is used as the binder resin.
- binder resin refers to synthetic polymers. Exclude pectin, agar, starch-based materials, cellulose-based materials, and natural gum-based (alginic acid-based) materials, which are well-known natural polymers. Also exclude items that remain semi-dry and moist even after drying (water is removed). Note that if the coating is not completely dried, there is a concern that it may cause corrosion if the coating is made of carbon steel.
- water-soluble or water-dispersible polymers that are composed of one polymer also include copolymers that are composed of two or more types of monomers.
- the individual monomers correspond to the monomers (1) to (4) above.
- At least one polymer from (1) to (4), or a copolymer made of two or more monomers, or both include copolymers made with other compounds.
- Other compounds refer to monomers of maleic acid, sulfonic acid, styrene, carboxylic acid, and salts thereof.
- Polymers and copolymers containing acrylate or methacrylate in their basic structure are considered to be monomers belonging to acrylate or methacrylate.
- Acrylate resin was chosen because it is a commonly available chemical and because it is easy to make water-based polymers. In addition, they are widely used, many of them are registered under the chemical drug regulations of each country, and they are easy to use.
- a suitable formulation of acrylates and solid lubricants enables coating agents with early drying properties for lubrication aid or for repairing lightly burned areas.
- the binder resin is dissolved in a solvent that is mostly water. Then, this is applied and the water is evaporated, which means it evaporates and evaporates, forming a film.
- PFAS fluorine from a group
- a polymer containing 95% or more of monomers belonging to acrylates and methacrylates, or a copolymer thereof is desirable to use.
- a product containing acrylate or methacrylate and copolymerized with other monomers is regarded as an acrylate or methacrylate-based polymer and satisfies the above-mentioned requirement of 95% or more.
- the setting of 95% or more means that it is mostly composed of acrylate and methacrylate polymers. It also means that less than 5% of other polymers are acceptable. In reality, the copolymer is almost 100% acrylate or methacrylate polymer.
- Metal soaps and alkaline soaps are composed of a combination of one or more types of higher fatty acids and metal elements (metal ions).
- Each of the metal soaps is preferably a compound consisting of a fatty acid selected from Group A and a metal element (metal ion) selected from Group B below.
- Each alkaline soap is preferably a compound consisting of a fatty acid selected from Group A and a metal element (metal ion) selected from Group C.
- ⁇ Group B Mg, Ca, Zn, Ba, Al
- Group C Na, K
- the metal soap of the present disclosure is utilized as a solid lubricant.
- the metal soap of the present disclosure is not intended to be used as a thickener that increases the viscosity of oil-based solvents. If the particle size of the metal soap is 5 ⁇ m or less, the metal soap can be used as a solid lubricant.
- the lubricated portion may generate heat, so it is preferable that the formed solid lubricant film has a high melting point.
- the solid lubricant coating preferably has a melting point of 100° C. or higher, and the above-mentioned preferred examples satisfy this condition.
- alkaline soaps Na salts and K salts of fatty acids
- alkaline soaps are preferably added up to 1% or less, even if they are not included. If alkaline soap is added to a water-based polymer, there is a concern that it will increase the viscosity of the water and increase the drying time. Moreover, it becomes difficult to apply, and there is a possibility that the application will be uneven.
- alkali metals improve the lubricating properties. It itself acts as a solid lubricant, and it is inevitable that the initial engagement position of the pin screw and box screw will be as shown in FIG. 5 in an actual well.
- Alkaline soap has a viscosity that makes it slippery when there is a little moisture, as we experience in daily life, so it is easy to achieve the above.
- the flash point of the drug is 60° C. or higher, preferably 150° C., and that the flash point cannot be measured and is treated as nonflammable.
- the environmental temperature at which the coating will be applied is between -50 and +50 degrees Celsius. You can assume that it will be used at temperatures between -60 and +60 degrees Celsius.
- the current highest temperature at the bottom of a well is exceptionally 250°C, and the highest temperature that can be assumed to be the temperature at the well base due to heat transfer is 150°C. For this reason, the temperature range was set as described above. To reduce the risk to zero, the flash point cannot be measured and the substance must be classified as nonflammable. This can be adjusted by selecting the lower alcohol and its blending ratio.
- the coating agent has a viscosity of 1000 mPa ⁇ sec or less. Setting the viscosity of the drug to be low is one means for promoting early drying. In addition, by lowering the viscosity of the coating agent and increasing its fluidity, it is possible to create a thin film by preventing it from being physically applied thickly. As a means of achieving early drying, it is preferable to reduce the viscosity to 1000 mPa ⁇ sec or less. You can also make it thinner by applying it with a brush or other techniques. However, since there are individual differences, it is preferable to lower the viscosity of the liquid and increase its fluidity to make it thinner. In addition, since the viscosity is low, the chemical can easily penetrate into partial repair areas such as touch-up, making it effective for repairs that fill in those areas.
- the lower limit of the viscosity is approximately 40 mPa ⁇ sec or more.
- the viscosity of water does not reach 1 mPa ⁇ sec. Viscosity tends to increase due to the influence of polymer materials. Therefore, the level is approximately 40 mPa ⁇ sec.
- the viscosity can be adjusted by adjusting the amount of water, the selection of monomers that make up the water-based polymer, the concentration of metal soap or alkaline soap, and the blending ratio, including the solvent.
- the viscosity of the coating agent is 1000 mPa ⁇ sec or less, the viscosity is low and it is easy to flow.
- the coating amount be within 30 minutes when left in the atmosphere at room temperature, and within 3 minutes when dried by blowing air at 1 m/sec or more. This can be said to be a suitable range in order to avoid undrying at the 6 o'clock position.
- any method of applying the chemical is acceptable, including brushing, spraying, dipping, hand painting, and machine painting.
- the object to be coated is tubular, it is better to apply it with a brush or spray while rotating it than to apply it while standing still. By doing so, you are also intensifying the drying process.
- the remaining amount of the coating agent that has not been formed into a film is evenly reapplied to the metal surface while rotating, which helps form a uniform film. In addition, it is possible to avoid accumulation at the 6 o'clock position.
- the conditions for the coating agent are those specified in the above-mentioned conditions.
- mild seizure occurs in the threaded area of a threaded joint of oil country tubular goods, use a grinder, file, paper, etc. to cure the seizure area. After curing, repair the area with chemicals to ensure lubrication again. For this reason, it is possible to perform partial repair by applying it only around the burnt-in area or over the entire surface.
- An oil country tubular threaded joint in which a lightly seized portion in the thread region has been repaired can be improved so that it can be tightened and unfastened again one or more times.
- the agent of the present disclosure may be applied onto an existing solid lubricant coating (which has never been tightened and loosened) to improve lubrication of a threaded joint of another oil country tubular product.
- the lubrication properties can be improved so that the belt can be tightened and untightened more than once.
- the thickness of the solid lubricant film formed using the coating agent described above is 10 ⁇ m or more and 100 ⁇ m or less, and the film hardness of the formed solid lubricant film is preferably soft with a pencil hardness of B or less.
- This film thickness is the film thickness at the stage when the chemical dries to become a solid lubricating film.
- the thickness of the film can be determined by, for example, cutting longitudinally at four points along the circumferential direction of the threaded portion (for example, four points at 90-degree intervals) and observing each cross section with a microscope. Execute. Through the observation, the thickness of each film at the thickest and thinnest parts of the film is determined.
- the film thickness may be estimated as follows. In other words, if the method of applying and drying the chemical is the same, the maximum and minimum values of the film thickness on the entire threaded part can be estimated by measuring the film thickness at a predetermined specific part with an electromagnetic film thickness meter. is also possible.
- film thickness differs depending on the case.
- the film thickness defined as a preferable range in the present disclosure: 10 ⁇ m or more and 100 ⁇ m or less refers to the following meaning. In other words, in the case of the former, it refers to the thickness of the film to be applied to areas that are still healthy, other than those that have been partially repaired due to damage.
- a uniform film thickness of about 10 ⁇ m to 50 ⁇ m would be sufficient to achieve lubrication.
- the viscosity is low, so no matter how much you strengthen the drying process or control the amount of application to a low level, the paint that cannot form a film tends to drip and move.
- this film thickness is defined as the thickness of the crest (thread portion) for both pin screws and box screws. Since this is the only area that can be checked non-destructively, that is, that the probe can be applied, it was chosen as the film thickness measurement point.
- the reason why the lower limit is set to 10 ⁇ m or more is also related to the fact that the size of solid lubricant graphite or metal soap is specified to be 5 ⁇ m or less. If the thickness is less than 10 ⁇ m, there is a high possibility that the solid lubricant film of the present disclosure will be destroyed when a load or torque is applied to the threaded portion during tightening and loosening of an oil country pipe screw. Furthermore, the absolute film thickness may not be sufficient to improve lubrication.
- the upper limit is that if it exceeds that limit, the screw gaps will become clogged with exfoliated pieces and powdery substances that are scraped off during tightening and loosening, rather than working to assist and improve lubrication. This is because there is a high risk of promoting burn-in. If it exceeds 100 ⁇ m, it will be scraped off during lubrication, and the peeled pieces will tend to cause seizure. There is also a possibility that the roots may peel off and burn. If the structure has threads, such as an oil country tubular thread structure, it cannot be denied that the coating agent tends to accumulate in the valleys of the threads, especially at the 6 o'clock position on a clock. Furthermore, due to the surface tension of the chemical solution, the corners of the crests of the thread structure tend to become thinner.
- the hardness of the formed solid lubricant coating is preferably a pencil hardness of H or less. This is because the solid lubricant film of the present disclosure is purposely made to have a soft film quality, and is intended to achieve lubricating properties on the assumption that it will be slightly scraped away when it is strongly hit.
- the film is preferably soft and has a pencil hardness of H or less. If the hardness exceeds H, and solid lubricant such as graphite or metal soap is added, it may become brittle and be uprooted due to the impact during tightening and unfastening. If they get stuck in the screw gaps, there is a high risk of seizure. It is preferably soft, with a pencil hardness of 2B or less, more preferably a pencil hardness of 4B or less.
- the film hardness is measured based on pencil hardness.
- the measurement method shall be as specified in JIS K 5600-5-4 (1999).
- the JIS standard states that this standard is a translation of the "ISO/DIS 15184, Paints and varnishes-Determination of film hardness by pencil test” standard. .
- the pencil hardness test method of the present disclosure is evaluated based on the provisions of the JIS standard.
- the evaluation method in the example was a weighted tongs test using the apparatus shown in FIGS. 6 and 7.
- the conditions simulated are the tightening and tightening tests that occur in actual wells and simulated wells, and the lubrication of the solid lubricant film is simulated to simulate tightening conditions as seen in Figures 3 and 5. It evaluates gender.
- FIG. 5 is an example of this. Therefore, when initially tightening with tongs, the pin screw and box screw begin to engage at their normal positions after several turns (about 6.3 turns in FIG. 3(a)) until the load is applied. Oil country tubular threads, like many thread-like structures, have a tapered structure (Figure 5). For this reason, the screws are finally engaged in a stable position (FIG. 3(b)). As shown in FIG. 5, if the image is exaggerated, the circled area will be severely damaged. That is, cracks, peeling, etc. always occur at a microscopic level.
- the pin screw 1a is set at a slight angle. Therefore, in relation to the threaded portion 2a of the box screw 2, at the tip of the pin screw 1a, near the middle of the thread of the threaded portion 2a of the box screw, and near the entrance of the threaded portion 2a of the box screw, The position where the pin screw hits tends to be severely damaged.
- the vicinity of the middle of the thread of the threaded portion 2a of the box screw is the vicinity of the position where the pin screw is inserted and comes into contact with the box screw, and the vicinity of the center of the pin screw 1a.
- the vicinity of the entrance of the threaded portion 2a of the box screw is the vicinity of the entrance of the box screw 2 when the pin screw is inserted.
- the initial set position of the pin screw cannot be set to the normal engagement position where it theoretically engages straight. Therefore, due to the rattling caused by this, the weight of the full-length pin, and the weight of the full-length pin, a non-uniform and uneven load is applied to the portion where the pin screw and the box screw first contact each other. As a result of this heavy load and unbalanced load, the solid lubricating film inevitably peels off or becomes powdery. These particles then get stuck in the screw gaps and seize up. We evaluated these effects using a new method that simulates them in the lab.
- solid lubricant composition consisting of a metal soap containing a small amount of graphite
- a tape-shaped secondary product that occurs due to the presence of graphite is generated during tightening and unfastening. Screw gaps tend to become clogged. After simulating this, it is necessary to clarify the upper and lower limits of the parameters. If this is not done, conventional tests using horizontal power tongs and vertical power tongs using short pins of about 1 m, which are often performed in laboratories, cannot be performed under mild conditions where the above-mentioned large loads and uneven loads are not applied. become. As a result, traditional laboratory tests may be deemed to pass even though they would fail in a real well. Therefore, the definition of parameters becomes meaningless.
- FIG. 6 is an overall conceptual diagram of the test method
- FIG. 7 is an enlarged view of the part related to the weight.
- vertical power tongs 4 are used for the weight tong test.
- the short screw 1 and the box screw 2 are tightened by the thread of the pin thread part 1a and the thread of the box thread part 2a.
- set the initial temporary tightening position so that half of the total number of threads of the pin thread part 1a is exposed from the box screw 2. .
- This is one of the causes of rattling.
- a weight 3 is attached to the upper end of the pin 1 on the opposite side from the tightening screw.
- the weight of the weight 3 is calculated based on the outer diameter and wall thickness of the actual length pin, and is equivalent to one to three actual length pins. If it is 9-5/8" 53.5#, it will be about 1 ton (2,200 Lb) per well, and if it is equivalent to 3 wells connected, it will be about 3 tons (6,600 Lb).
- the equivalent of 1 well is assumed to be an onshore well, and 3 wells. The equivalent is assumed to be tightened in offshore wells.
- the weight 3 has an insertion rod 13 welded to the weight main body 3A at an axially symmetrical position of the weight. Insert the insertion rod 13 into the pin 1 and attach the weight to the upper end of the pin 1. Through holes 1d and 13a are made in advance in the pin 1 and the insertion rod 13. A piercing rod 12 is inserted and set into the through holes 1d and 13a in order to integrate the weight 3 and the pin 1. A swivel type hook 11 is welded to the center of the upper axis of the weight 3, and the weight is suspended from a hanging device 20 on the ceiling via a hanging chain 21. When tightening, apply a weight to the box screw and tighten at 5 to 20 rpm until torque is reached. The initial temporary tightening position and high-speed rotation during tightening and untightening are simulations of wobbling. Once the torque is established, reduce the rotation speed to 0.5 to 2 rpm and tighten to the tightening position.
- the load of the weight 3 may be applied or not.
- the base film Mn phosphate chemical conversion film or electroplated film
- the clamp is tightened and untightened in this state, the underlying Mn phosphate layer and the masking made only of electroplating will be burned in, making it possible to create a sample with good reproduction.
- the weight tongs test method shown above was also used.
- Example 1 How to prepare metal soap
- the conditions for mixing the metal soap were selected based on how it was mixed into the liquid.
- the water-based polymer, solid lubricant, and water were mixed in a weight ratio of 40:20:40.
- Ethanol was mixed here at a weight ratio of 1 to 100 of the total drug weight.
- a small amount of aqueous ammonia was added to adjust the pH.
- a water-based polymer (binder resin) 10 parts by weight of acrylic acid was prepared with respect to 100 parts by weight of vinyl acetate, and a copolymer of vinyl acetate and acrylic acid was used as a monomer. This resulted in 100% polymer belonging to acrylate.
- the solid lubricant used was one consisting of metal soap and graphite, each with a particle size of 5 ⁇ m or less. At this time, the weight ratio of metal soap to graphite was 96:4. This indicates 4% by weight of graphite.
- To prepare these prepare a mixture of each monomer to make a water-based polymer "vinyl acetate and methacrylic acid copolymer" in water, and add metal soap and graphite to disperse it.
- This example shows various studies conducted on a method for uniformly dissolving metal soap and graphite in an aqueous polymer dissolved in a water-based solvent. That is, the degree of homogeneous dispersion was investigated in a series of studies of mixing with industrial ethanol using the method shown below. Note that Ca stearate was used as the metal soap here.
- Condition 1 is an example in which metal soap and graphite were directly added to the basic drug and stirred according to the above mixing ratio. This is an example of not using any industrial ethanol. Under condition 1, the mixture was not thoroughly mixed, and some metal soap and graphite floated on the surface and aggregated together, making it impossible to mix well and homogeneously. Condition 1 gave results that supported the conventional knowledge that these solid lubricants have water repellency and are insoluble in water.
- Condition 2 is to add metal soap and graphite to the basic chemical according to the above mixing ratio, stir it, and mix 2.5 parts of industrial ethanol to 100 parts of water in a Vol/Vol ratio. It was poured into a solvent. This corresponds to 1 part by weight when the final basic composition of the above-mentioned coating solvent "aqueous polymer, solid lubricant, water" is 100 parts by weight. In this case, the metal soap and graphite were not thoroughly mixed and some were seen floating on the surface and clumping together, so it was not possible to mix the metal soap and graphite homogeneously. Condition 2 indicates that even if ethanol is mixed later, the metal soap and graphite cannot be mixed well.
- Condition 3 is the amount of industrial ethanol: 2.5 parts per 100 parts of water, and the metal soap and graphite are stirred in the industrial ethanol in a separate container, that is, after they are mixed homogeneously, they are added to the basic agent. This is an example of adding the liquid to the water and stirring it.
- Condition 3 can be said to be an example of almost homogeneous mixture.
- Metal soap and graphite are said to be insoluble in water.
- alcohol industrial ethanol; ethanol is the main component
- Condition 4 is an amount of industrial ethanol of 0.5 to 100 of water, and metal soap and graphite are sufficiently stirred in the industrial ethanol in a separate container. However, the amount of alcohol was small, and although the metal soap and graphite were dissolved, a small amount did not appear to be mixed in when added to the basic drug.
- Condition 4 is an example in which 2 parts of industrial ethanol were subsequently added to the basic chemical and stirred. This is an example of a solution that was pre-dissolved in industrial alcohol and then added to a water solvent to make it almost homogeneous. Furthermore, it was recognized that by adding only industrial ethanol 2 to the base chemical, dissolution proceeded further and homogeneous dispersion was achieved.
- Condition 5 was an amount of industrial ethanol: 2 parts per 100 parts of water, and the metal soap and graphite were sufficiently stirred in a separate container in the industrial ethanol, and then added to the basic agent. This is an example in which 0.5 of industrial ethanol was subsequently added to the basic chemical and stirred.
- Ca stearate which is a metal soap, and graphite were already homogeneously mixed in industrial ethanol:2. Therefore, even if industrial ethanol is further added from that state, the metal soap Ca stearate does not change in particular and can be said to be an example of homogeneous mixing.
- Example 2 Examination of early drying properties, application amount, solid lubricant particle size, drying method, etc.
- the study group of Example 2 is an example in which the structure of an oil country tubular screw was coated and the quality was judged based on the degree of dryness.
- Example 2 the mixing ratio of alcohol and aqueous ammonia, the different types of alcohol, and the sizes of metal soap and graphite were investigated. That is, the following individual chemicals were systematically prepared under different conditions, and their early drying properties were investigated.
- the weight ratio of water-based polymer, solid lubricant, and water, as well as the added amounts of lower alcohol and aqueous ammonia, are expressed as a weight ratio to 100 parts of water. Note that ammonia water (concentrated ammonia water of about 28% to 30%) was added so as to be within the pH range indicated by the water-based polymer.
- Solid lubricants consist of metal soap, alkaline soap, and graphite.
- water-based polymer binder resin
- a copolymer prepared by containing 100 parts by weight of acrylic acid and 6 parts by weight of polyvinyl alcohol as a monomer was used.
- the respective mixing ratios were systematically varied and studied as shown in the study content of Example 2.
- Polyvinyl alcohol is, for example, saponified polyvinyl acetate obtained by polymerizing vinyl acetate monomer with poval.
- the oil country pipe screws were made of carbon steel, L80 grade, 5.5"23#, JFEBEAR TM pin screws, and were machined at both ends with a short length of 700-1000 mm. It was made of oil country tubular screws.
- a general paint brush Japanese standard for brushes: No. 20: brush width 50 mm
- the short pin was rotated the same number of times by two rollers.
- the two rollers come into contact with the 5.5" 23# pin screw at roughly the 5 o'clock and 7 o'clock positions on a clock.
- the cross-sectional center position is set as the center
- the upper position in the vertical direction is determined as the 12 o'clock position
- the lower position is determined as the 6 o'clock position
- the right position in the horizontal direction is determined as the 3 o'clock position
- the left position is determined as the 9 o'clock position.
- This area is unavoidably coated because the brush goes around.I applied 6 to 9g per end.
- the amount applied was estimated by the change in the weight of the brush.However, from the 6 o'clock position, The amount of dripping of the coating agent is not taken into account.
- the coating weight was calculated from the difference in brush weight. However, since it contains volatile components, the amount that evaporates cannot become a film constituent material, so strictly speaking, it cannot be called coating weight. However, in the present disclosure, the difference in the weight of the brush is regarded as the application weight and organized. However, since it is a coating agent with low viscosity and high fluidity, especially on the side where it was left unattended after application, it felt like half-dry paint had accumulated at the 6 o'clock position. Ultimately, there will be some dripping from the 6 o'clock position, but we ignored that amount in the application amount.
- the viscosity of the liquid was prepared at approximately 600 to 900 mPa ⁇ sec and did not change significantly, except for some exceptions, so that the influence of other conditions could be determined.
- the exceptions are cases where the mixing ratio of the solvent is increased, that is, coating chemicals are mixed thinly with water-based solvents, and cases where the viscosity is increased by decreasing the amount of water or increasing the amount of water-based polymer. This is an example of a case in which The results and details of the conditions are shown in Tables 1 and 2.
- the examples studied in 2-1 to 2-6 are copolymers of acrylic acid and polyvinyl alcohol (poval; saponified polyvinyl acetate obtained by polymerizing vinyl acetate monomers), and when acrylic acid is 100 parts by weight, This is an example of studying the early drying properties of a water-based polymer containing 6 parts by weight of polyvinyl alcohol.
- the viscosity of the coating agent is an example of using a low viscosity agent of 700 to 850 mPa ⁇ sec.
- the mixing ratio of water-based polymer, solid lubricant (metallic soap and graphite), and water is 35:15:50, and only a small amount of ammonia is commonly added to adjust the pH.
- No. 2-1 is a comparative example that does not contain metal soap, graphite, or alcohol. This serves as a standard for evaluating early drying. In response to this, it was determined whether early drying was possible and whether parameters other than early drying were satisfied.
- No. 2-2 is a case in which there is no metal soap, no graphite, and industrial alcohol is added to the solvent. In other words, this is an example in which no metal soap or graphite is added. It is treated as a comparative example because it does not contain graphite or metal soap for lubricating properties.
- No. 2-2 is an example in which the drying time is faster because alcohol volatilization is used, but the target value of air drying of 5 minutes is not achieved, and this is a comparative example. No.
- No. 2-4 is an example with metal soap, no graphite, and alcohol.
- No. 2-5 is a case without metal soap, with graphite, and with alcohol. Although it passes the drying time criteria, from a lubrication perspective, the blending ratio of the solid lubricant is not within the specified range, so it is considered a comparative example.
- No. Conditions 2-5 using only graphite also cleared the criteria for drying time. There was a tendency for the drying time to be slightly faster. Although the reason is not clear, it is possible that the fine pore-like structure of graphite is effective.
- the blending ratio of the solid lubricant is not within the specified range of the present disclosure, and the lubricating properties of graphite alone are unclear, so this is treated as a comparative example (reference example).
- No. 2-6 is an example of the present invention with metal soap, graphite, and alcohol. This shows that early drying can be achieved by designing a combination of solid lubricants, alcohol, ammonia, etc. within the specified range of the present disclosure.
- No. Examples 2-7 to 2-18 are cases in which the water-based polymer consists of a methacrylic acid/styrene copolymer. Further, the copolymer has a mixing ratio of 100 parts by weight of methacrylic acid and 9 parts by weight of styrene. Since it is a copolymer, this binder resin component is an example of handling 100% methacrylate. Additionally, this case study considered the type of soap, type and concentration of alcohol, etc.
- the viscosity of the coating agent is at a level of 350 to 550 mPa ⁇ sec, and this is an example of using a low-viscosity agent. No.
- the mixing ratio of water-based polymer, solid lubricant (metal soap and graphite), and water is 30:20:50.
- a trace amount of ammonia is commonly added to adjust the pH. This is an example of a study in which the size of metal soap and graphite, the type of alcohol, and the mixing ratio were systematically changed. Note that these formed films had a pencil hardness of 4B. The flash point changes depending on the amount of alcohol added.
- No. 2-7 is the standard that does not contain metal soap, graphite, and alcohol.
- the criteria for judgment are whether early drying was achieved and whether parameters other than early drying were satisfied.
- No. 2-8 to 2-9 are study examples in which the size of Ca stearate, which is a metal soap, was changed.
- No. Examples 2-8 to 2-9 are examples of the present invention that both meet the standard value for early drying.
- the reason No. 2-9 dries faster is that the particle size of the metal soap and graphite is 1 ⁇ m. It is presumed that this is because the particle size was finer than the 5 ⁇ m particle size of No. 2-8, and the surface area increased, promoting early drying.
- No. 2-10 and 2-11 are examples in which the amount of metal soap and the amount of industrial ethanol added were increased.
- No. 2-10 is an example of the invention in which the upper limit of the amount of metal soap added was dissolved with a large amount of industrial ethanol.
- No. Sample No. 2-10 has a fast drying time and satisfies the drying criteria. However, although the flash point drops to about 60° C. by increasing the amount of ethanol, it remains at the preferred lower limit of the flash point, which corresponds to the example of the present invention.
- No. No. 2-11 is a case in which the drying time is satisfactory, but the flash point falls below the preferred lower limit standard and has a flash point in the low temperature range.
- Example 3 Effect of various conditions on lubricity (touch-up partial repair characteristics)
- oil country tubular screws lubricated with an actual solid lubricant coating were intentionally and artificially seized.
- curing was performed by scraping off the burnt areas using a grinder or sandpaper. This is an example in which lubrication was then examined by applying a candidate coating agent, which is considered in this disclosure, to that part and other areas.
- the conditions are shown in Tables 3 and 4.
- No. Nos. 3-1 to 3-5 are OCTGs made of carbon steel Q125 material, 9-5/8" 53.5 # size, and have JFELION TM threads.
- the solid lubricant coating of the box screw and the solid lubricant coating of the pin screw correspond to 3-B2 and 3-P2 in Tables 3 and 4, respectively.And, the one in which seizure was artificially caused.
- the evaluation was carried out using weight tongs, and the tightening was carried out by applying a load of 1 ton with the weight.In other words, a load equivalent to the weight of one full-length pin was applied. Become.
- No. 3-1 to 3-2 are examples of the present invention in which touch-up-like partial repair was possible using a drug within the scope of the present disclosure, and tightening and loosening could be performed three or more times.
- the metal soap + graphite-based agent filled the curing area with a film without creating a tape-like secondary product, contributing to the restoration of high lubrication.
- No. 3-3 is an example in which the size of the graphite is larger than the preferred specification, and the one time was improved so that it could be further tightened and loosened. However, the improvement effect is not large.
- No. 3-4 is a comparative example in which too much solid lubricant was used, that is, too much graphite was blended. No.
- No. 3-6 to 3-7 are for drugs within the scope of the present disclosure. Both had partial touch-up repairs. The former is a case in which tightening and unfastening can be performed three or more times. The latter improved only twice. Both correspond to examples of the present invention.
- Graphite filled the curing area without creating tape-like secondary products and contributed to the restoration of high lubrication. No. It is presumed that the difference between 3-6 and 3-7 is due to the difference in the size of graphite. The reason why the improvement effect in the latter case is smaller is presumed to be due to the aggravation of the effect of clogging the screw gap due to the larger graphite.
- No. 3-8 is an example in which the proportion of solid lubricant is high. No.
- 3-9 is an example in which the proportion of water-based polymer is high.
- No. 3-10 is a case where there is a lot of water.
- No. 3-8 to 3-10 are comparative examples in which the stability of the solid lubricant film was not good and the necessary lubrication could not be secured, resulting in seizure even after repair.
- Examples 3-11 to 3-15 are made of stainless steel: UHP TM -15CR-125 manufactured by JFE, are oil country tubular goods of 9-5/8"47.0# size, and are intended for JFELION TM threads. Cases No. 3-11 to 3-15 have different solid lubricant coatings on the box screw and pin screw, and correspond to 3-B3 and 3-P3 in Table 3 in that order. In the same way, we prepared a product in which seizing was artificially caused. The evaluation was carried out using weighted tongs, and tightening was carried out by applying a load of 2.5 tons with the weight.
- the water-based polymer is ethylene/methacrylic acid copolymer resin (30:100).However, ethylene here refers to ethylene oxide. It refers to the part by weight of ethylene polymerized to methacrylic acid using a random copolymer of methacrylic acid and propylene oxide.
- No. 3-11 to 3-12 are cases where drugs within the scope of the present disclosure were used.
- No. 3-11 to 3-12 are examples of the present invention, where touch-up-like partial repairs were possible and tightening and unfastening could be performed three or more times.
- Graphite filled the curing area without creating tape-like secondary products and contributed to the restoration of high lubrication.
- No. 3-13 is a case where there was too much graphite. This is a comparative example where there is a concern that even if the paint is mixed with alcohol beforehand and is added to a water-based composition, it tends to form lumps.
- No. 3-14 is a case in which no metal soap was added and is a comparative example. No.
- Example 4 Effects of each condition in terms of lubricity (characteristics of overall lubrication improvement)
- Example 4 No. In cases 4-1 to 4-5, two parallel comparative tests were conducted on the solid lubricant coating used in Example 3 above. One method is to simply conduct a tightening/unfastening test and investigate the number of times the tightening/unfastening is performed. Then, before tightening, the agent of the present disclosure is uniformly applied to the surface, and a weight tongs test is performed to investigate the number of times of tightening and unfastening, and the presence or absence of improvement can be determined by the change in the number of times. . This time, we did not intentionally create burn-in and instead formed a uniform film. The results are shown in Tables 7 to 10.
- No. Examples of 4-1-B, 4-1-P, 4-1-BP, and 4-1-BP2 are all No. Oil country tubular threaded pipes of the same size and grade as those used in cases 3-1 to 3-5 were used.
- No. 3 of Example 3 is used. This is a study example using the condition 3-1. The results also show how the agent of the present disclosure was applied as a lubrication aid onto the already existing solid lubricant coating (3-B2, 3-P2 in Table 3).
- No. 4-1-B, 4-1-P, 4-1-BP, and 4-1-BP2 were performed using a weight tongs test using a 1 ton weight. No.
- 4-1-BP2 is a condition in which the solid lubricant film on the pin screw side: 3-P2 is replaced with the auxiliary lubrication film of the present disclosure.
- the auxiliary lubrication film also functions as the solid lubricant film itself on the pin screw side, and it can be seen that lubricating properties can be achieved.
- Example 4-3-B No. Similar results were obtained in Example 4-3-B. In other words, it has been found that lubrication can be improved by forming a top coat on the box screw side with a coating agent within a specified range that is expected to have a lubrication-assisting effect.
- No. 4-4-B-0, 4-4-B-0.5, 4-4-B-1.0, 4-4-B-3.0, 4-4-B-5.0, 4- Case 4-B-8.0 is a case in which a coating agent within the specified range was expected to have a lubricating effect on the box screw side. In these cases, the graphite content is 0.0%, 0.5%, 1.0%, 3.0%, and 5.0% based on the weight of the total solid lubricant. This is the result of a comparative investigation under the conditions of % and 8.0%.
- the present disclosure can also take the following configuration.
- a coating agent for forming a solid lubricant film by applying it to a metal surface The main ingredients are solid lubricant, binder resin, and solvent,
- the above-mentioned solvent has water as a main component, and a lower alcohol having 3 or less carbon atoms is added to the water as an additive, and the volume of the above-mentioned additive is 0.5 or more and 10 or less per 100 volumes of water, 95% or more of the volume of the solvent is composed of the water and the additive
- the solid lubricant contains graphite and metal soap in an amount of 95% or more of the total solid lubricant component weight, Furthermore, the solid lubricant contains an alkali soap in an amount of 0% or more and 1% or less of the total solid lubricant component weight,
- the graphite is 0.5% or more and 5% or less of the total solid lubricant in terms of weight ratio
- the binder resin is a water-soluble or water-dispers
- Ammonia water is further added as the above additive.
- the binder resin accounts for 30% or more and 40% or less of the total weight of the drug;
- the solid lubricant accounts for 10% or more and 20% or less of the total weight of the drug,
- the solvent accounts for 40% or more and 50% or less of the total weight of the drug.
- a solvent component at least a lower alcohol among a lower alcohol and aqueous ammonia is added as an additive to the water constituting the solvent, and the lower alcohol is one or more types and has a carbon number of 3 or less.
- the volume of the lower alcohol is 0.5 or more and 10 or less per 100 volumes of water constituting the solvent, The volume of the ammonia water is 0 or more and 5 or less per 100 volumes of water constituting the solvent.
- the lower alcohol is selected from methanol, ethanol, isopropyl alcohol, normal propyl alcohol, and industrial ethanol.
- the average particle size of the graphite is 5 ⁇ m or less, The average particle size of the metal soap is 5 ⁇ m or less.
- the water-soluble or water-dispersible polymer constituting the binder resin is a polymer composed of a single monomer among the monomers listed in (1) to (4) below, or a polymer composed of a single monomer listed in (1) to (4) below.
- the above-mentioned metal soap includes a fatty acid selected from Group A below and a metal selected from Group B below.
- the alkaline soap includes one or more types of alkaline soaps, which are compounds consisting of a fatty acid selected from Group A below and a metal element selected from Group C below.
- Group A stearic acid, behenic acid, lauric acid, 12-hydroxystearic acid, oleic acid, montanic acid
- Group B Mg, Ca, Zn, Ba
- Group C Na, K
- the coating agent of the present disclosure which has a flash point of 60° C. or higher or is nonflammable.
- the coating agent of the present disclosure wherein the viscosity of the agent is 1000 mPa ⁇ sec or less.
- a method for producing a coating agent of the present disclosure comprising: The metal soap is prepared by dispersing and turbidizing the metal soap in the lower alcohol and then adding it to water as a solvent.
- An OCTG repair method for repairing a lubricating film on a threaded portion of an OCTG comprising: After curing the area where seizing has occurred among the threaded portions of the oil country tubular goods, the coating agent of the present disclosure is applied to at least the curing portion. (15) Applying the coating agent of the present disclosure onto the solid lubricant coating of an oil country tubular goods pipe in which a solid lubricant coating is formed on the threaded portion.
- the solid lubricant film is composed of a solid lubricant dispersed in a binder resin
- the solid lubricant graphite and metal soap account for 95% or more of the total solid lubricant component weight
- the solid lubricant contains an alkali soap in an amount of 0% or more and 1% or less of the total solid lubricant component weight
- the graphite is 0.5% or more and 5% or less of the total solid lubricant in terms of weight ratio
- the binder resin is a water-soluble or water-dispersible polymer
- the polymer is a polymer or copolymer containing a monomer belonging to acrylate or methacrylate in an amount of 90% or more of the total weight of the binder resin.
- the average particle size of the graphite is 5 ⁇ m or less, The average particle size of the metal soap is 5 ⁇ m or less.
- the metal soap accounts for 0.5% or more and 5% or less of the total solid lubricant by weight.
- the water-soluble or water-dispersible polymer constituting the binder resin is a polymer composed of a single monomer among the monomers listed in (1) to (4) below, or a polymer composed of a single monomer among the monomers listed in (1) to (4) below.
- Monomers mainly composed of acrylates, methacrylates, and their individual derivatives (2) Acrylates, methacrylates, and their individual derivatives, as well as alkyl esters, vinyl esters, styrene esters, carboxylic acid esters, and their respective derivatives.
- Monomers integrated with monomers containing individual derivatives (3) Monomers grafted to (1) and (2) above (4) Monomers of one or both of vinyl compounds and urethane compounds, A monomer (20) that is integrally formed with at least one or more monomers from (1) to (3); as the metal soap, a fatty acid selected from Group A below and a metal selected from Group B below; Contains one or more types of metal soap, which is a compound consisting of elements,
- the alkaline soap includes one or more types of alkaline soaps, which are compounds consisting of a fatty acid selected from Group A below and a metal element selected from Group C below.
- the solid lubricant coating has a thickness of 10 ⁇ m or more and 100 ⁇ m or less, and is soft with a pencil hardness of B or less.
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Abstract
Description
本開示は、例えば、既存の固体潤滑被膜に対し、更に1段階レベルアップした潤滑性が必要な場合に使用される。すなわち、本開示は、潤滑性の向上や、予防的な意味を含めて焼き付きを避ける目的で、既存の固体潤滑被膜の上に塗布することも含む。単に、本開示の固体潤滑被膜だけで、潤滑を実現させる場合も対象とする。
例えば、油井管が炭素鋼系の場合、ねじ面にリン酸Mn化成処理膜を下地として形成する。また、油井管がステンレス・高合金系の場合、ねじ面にCuめっきをはじめとする電気めっき膜を下地として、ボックスねじ(雌ねじ)側に施す。その後、ボックスねじ、ピンねじのいずれか一方かあるいは両方に、潤滑用コンパウンドを塗布して潤滑性を付与する。
湿式のコンパウンドは濡れた潤滑膜を形成する。これに対し、固体潤滑被膜による潤滑技術は、ドライ技術とかグリースレス技術と呼ばれる。固体潤滑被膜による潤滑技術は、石油/ガスの掘削現場、生産で使われる油井管の潤滑を達成できる重要な技術の1つになりつつある。
ここで、本明細書におけるピンねじの実長とは、10m以上を指す。
こういった補修の場合、従来の潤滑用コンパウンド、すなわち、Pb、Zn、グラファイト等の重金属群が入ったコンパウンドだけを塗って対応することはほとんどない。補修には、焼き付き防止(Anti-seize)のスプレー、ペースト、コンパウンドの市販されている補修用の商品群(補修剤)を使う。焼き付き防止(Anti-seize)の潤滑剤の分野は裾野が広い。例えば、単なる鉱物油だけの構成から、鉱物油などに金属粉(Zn系、Ni系)を分散させものや、潤滑剤(黒鉛、MoS2、BN、PTFE、シリコン)などを分散させたりするものなど、数多くある。
モリコートの油井管分野での活用方法は、普通は、潤滑が異常の時だけに、次のように用いられる。すなわち、井戸の締付け現場で、焼き付き箇所を養生した後に、井戸元でのタッチアップの際に、モリコートを管に塗布するのが一般的な使い方である。ただし、モリコートは、高度な潤滑性を保証するような潤滑剤であって、補修部をパテ的に埋めきるようなものではない。モリコートは、あくまでも補修材である。
この井戸元でのタッチアップは、ねじのシール性を維持することを目的として、ねじ山領域の軽度な焼き付きの場合の救済処置である。しかし、シール部分が少しでも焼き付く場合には救済しえない。また、事前に潤滑が不十分と予想される場合には、予防的に、モリコートを塗って、全面的に潤滑性をワンランク向上させて対応する使い方がなされる場合もある。
最近では油井管の強度・硬度が高くなってきたこともあって、その懸念が問題視されるようになってきた。例えば、非特許文献1には、Ni基合金の油井管に、MoS2を含むスプレーからなる潤滑剤を塗布すると割れた、という報告が記載されている。また、石油/ガスのエンジニアの中では、MoS2がH2Sに変化して、結果として、水素脆化になる懸念が高くなるという考え方も流布している。よって、井戸元でのタッチアップの目的で使う薬剤は、MoS2を含有するモリコートの使用を避けたいというニーズが高い。
発明者の調査によると、潤滑用コンパウンドを使うケースと違って、固体潤滑被膜での潤滑は、軽度な焼き付きが起こりやすい傾向がある。
また、固体潤滑被膜は、Dry被膜と呼ばれるように、乾いた固体潤滑膜である。井戸元でのタッチアップにおいて、ペースト状又はスプレー状のモリコートを使うとなれば、固体潤滑被膜の場合、別の課題がある。
また、フッ素溶剤(HFE他)に分散した、PFASを含むフッ素樹脂は、低沸点であるがゆえに速乾性がある。そして、そのフッ素樹脂は、従来のVOCと違って、引火点は高く、火災や爆発を起こさないので安全に、かつ、早期に乾燥できる膜を提供できる。しかし、2021年4月のTSCAでのPFAS利用に対して大幅に規制がかかった事実から、PFASを含む製品は実質的に使えないと判断できる。
また、井戸元でのタッチアップとは別に、次のような使用のケースがある。すなわち、タッチアップで期待されるような部分補修ではなくて、既に存在している固体潤滑被膜自体の潤滑性特性を、一段階向上させることが必要とされるケースがある。これは、従来の下地被膜に、コンパウンドで締め付ける技術にはない観点である。なお、下地被膜は、化成処理や電気メッキで形成される。
特に、大径・厚肉材では、締付トルク値が大きくなり、ピンねじの重さも重くなる。したがって、実際のフィールドで、立てて吊られながら締付けられる状況では、固体潤滑被膜が根こそぎ剥離する等のダメージが起こることがある。
この場合、下地膜を考慮しない場合、固体潤滑被膜の全体の構造は、2層膜構造となっている。下地膜を考慮しない場合とは、例えば、リン酸化成処理膜や電気めっき膜を考慮しない場合である。
また、全面的な2層構造の例は、数多くある。例えば、特許文献3、4が例示できる。これらは、全面的な2層構造である。
特許文献3は、固体潤滑剤を入れない固体潤滑被膜(バインダー樹脂のみ)を表層に、固体潤滑剤を入れた通常の固体潤滑被膜を下層に形成したものである。ただし、特許文献3での2層化は、固体潤滑剤が入ることで固体潤滑被膜が多孔質になって防錆能力に欠ける点を、最表層(固体潤滑剤無しの固体潤滑被膜)で覆う。これによって、特許文献3では、耐食能力を高めることを目的としている。
しかし、過去の先行文献において、その技術思想は見いだせなかった。
特許文献5には、UV硬化膜の上にアクリルシリコン樹脂が形成され、アクリルシリコン樹脂は、固体潤滑剤として金属石鹸を含むことが例示されている。また、ラッカーベースの吹き付け式のアクリルシリコン樹脂水性及び油性が例示され、油性がよいと記載されている。すなわち、積極的に、水性のバインダー樹脂を使用するものではない。
特許文献6には、粘稠液体又は半固体の潤滑被膜と、その上に形成された乾燥固体被膜とを有し、いずれの膜も固体潤滑剤を含むことが記載されている。
特許文献7には、熱可塑性樹脂として、アクリル樹脂が例示されている。不揮発性成分に、金属石鹸やワックスを一例として含むことが記載されている。また、ワックスは、焼付き防止効果だけでなく、潤滑被膜形成用組成物の流動性を低下させ、被膜強度を向上させるのにも有効であることが記載されている。また、動物性、植物性、鉱物性及び合成ワックスのいずれも使用できることが記載されている。
特許文献8には、縦型のパワートングを使い、かつ、ミスアライメントを想定して、7”サイズの短尺ピンを使って、初期セットを角度6度で試験したと明記がある。
ここで、本明細書における短尺ピンの長さは、API RP 5C5 2017のねじ試験に使用されるピンの一般的な長さを指す。具体的には、その長さは、1m前後である。
特許文献9には、縦型のパワートングを使い、9-5/8”サイズの短尺ピンを使って、ミスアライメントを5度で試験評価した事例である。
非特許文献2は、縦型のパワートングを使い、短尺ピンの締め付け側の逆側の先端、つまり、ピンを立てて締め付ける際に、ピンの上端部に5kN(約500kg)の重りを乗せて潤滑を評価した論文である。
本開示でいう、金属石鹸とは、アルカリ金属以外の金属イオンと高級脂肪酸の塩とする。アルカリ石鹸は、日常的に使う、いわゆる石鹸であり、アルカリ金属のイオンのうち、NaイオンあるいはKイオンと高級脂肪酸の塩と定義する。NaとK以外のアルカリ金属の塩は、金属石鹸として扱う。
この場合、金属石鹸自体は、撥水性を持ち、水に不溶であるので、水系溶媒に混ぜることが困難であるといわれている。金属石鹸は、同時にアルコール群にも不溶であるといわれている。金属石鹸がやや溶けるとされるのは、VOC(揮発性有機物)で、しかも、シンナーと呼ばれる薬剤群である。しかし、この薬剤群は、健康に有害とされることが多い、トルエン、キシレン、ベンゼン、ミネラルスピリッツに属するVOC群、及び、エーテル群、及び、広く鉱油と呼ばれるような油に分類される薬剤として知られている。
また、特許文献6には、水系単独の系、水+揮発性有機溶剤の系、及び紫外線硬化樹脂を使う系が、例示されている。このうち、後ろの2点は早期乾燥が可能である。しかし、最初の1つ目の水系単独系のポリマーでは、水をなんらかの方法で蒸発させる必要がある。しかし、特許文献6にはその方法が明示されていない。
更に、その薬剤を使って固体潤滑被膜を製膜する際に、溶剤としての水が揮発しにくい、蒸発には時間がかかるという課題もあった。
更に、井戸元でのタッチアップによる潤滑特性の特性評価は、従来の単純なラボ実験や模擬で評価できるレベルものではない。このため、井戸元でのタッチアップによる潤滑特性の特性評価は、想定できうる最も厳しい条件でも対応できるように設定することが好ましい。
つまり、固体潤滑被膜を使う油井管ねじの潤滑の評価の場合、単に1m程度の短尺ピンを使った従来のラボでの締付け試験でNG判定のものは、実際の井戸でもNGとして判定できる。しかし、発明者は、ラボで1m程度の短尺ピンで評価してOKのものが、実際の井戸でOKであることを保証してくれない、との知見を得た。しかしながら、従来、この事実に注目して、固体潤滑被膜の潤滑性を、実井戸に沿った条件を想定して可否判断したものは非常に少ない。すなわち、過去の先行文献で、固体潤滑被膜のパラメータの上下限の規定範囲を設定したリ、説明する際に、この点を考慮されたものは、きわめて少ない。
油井管ねじの構造はテーパーねじ構造で、ピンねじが差し込む形でボックスねじに入っていく。軽量で短い短尺ピンならば取り回しが容易で、短尺ピンは真っ直ぐセットされることが多い(図4(a))。そのときに、テーパーねじ構造の不完全ねじ部分に、「遊び(ガタ、余裕)」があるが、短尺ピンの場合には、手締めで、ショルダー近くまで締めることが可能になる(図2、図4(b))。不完全ねじ部分とは、例えば、ねじ山が完全ではなく、ねじ高さ、ねじ谷が小さいところである。
一方、非特許文献2は、縦型のパワートングを使い、短尺ピンの上端に5kNの重りを乗せて潤滑を評価した論文である。非特許文献2は、7”29#のピンのトルク・ターン・チャートから判断すると、実長ピン1本分、つまり約40フィート(約12m)のピンの重量を印加したことを意図していると思われる。しかし、トルク・ターン・チャートから判断すると、図3(a)ではなくて、図2(a)に近い締付け挙動となっている。すなわち、初期セット位置が、手締めでピンねじが露出しないレベルまで締め付けて、ピンねじとボックスねじが十分に噛み合った状態から、締付けされた評価試験と判断される。このため、非特許文献2では、実際の井戸で発生する状況を模擬出来ていない。
本開示は、例えば、油井管ねじ継手の潤滑で、油井管ねじの構成要素におけるねじ山部分とシール部分のうち、ねじ山部分だけに軽度な焼き付きが起きた場合に、井戸元で行う補修に用いる薬剤に関わる。本開示は、例えば、焼き付き部分を、グラインダー、サンドペーパー、やすり等で削って養生したあとに、養生部分を含めて、その領域にタッチアップの目的で塗布することを目的とする薬剤に関する。
これらを実現するにあたり、上述の従来技術群から課題として抽出し、次のような条件を考えて、本開示の発明をなした。
エコロジーの観点、作業者の安全、火気厳禁でも使えるようにするため、水に溶けるものをベースに薬剤設計する。同時に、膜化するために、溶剤の水を早期に乾燥可能とする。
固体潤滑剤に、Pbをはじめとする有害とされる重金属を使わない。
また、バインダー樹脂の構成要素として、PFAS(PFOS、PFOAを含めた、フッ素含有アクリル基)を含む薬剤や、地球温暖化係数が高い代替フッ素系溶剤を一切使用しない。
ここで、本開示では、水溶性若しくは水分散性のポリマーを使い、膜が乾いたときには、軟質のポリマー系樹脂膜になるバインダー樹脂に対して、固体潤滑剤を分散分布させる設計である。さらに、固体潤滑剤として、金属石鹸と黒鉛を共に混入させたところに特徴の一つがある。
黒鉛は広く潤滑剤として使われている。しかし、油井管ねじのような溝がある構造で、且つ固体潤滑被膜のような乾いた膜の状況においては、潤滑成分の黒鉛が押し付けられて変形した際の「逃げ道(延伸して変形する方向)」が限られている。このため、ねじ継手を強い力で締付けたときには、ねじ溝に沿って、黒テープ状の薄片ができやすい。そして、それが、ねじ同士の間隙に詰まって焼き付きを引き起こしやすい。本発明者の観察によると、例えば、黒鉛(固体潤滑剤)とエポキシ樹脂(バインダー樹脂)からなる膜について、黒鉛の調合分率が多い時には、次の知見を得た。すなわち、締付け締戻しの際に、黒鉛とバインダー樹脂からなるテープ状破片群が、ねじの間隙に詰まってしまって、焼き付きを引き起こす事例が散見された。
このため、本開示では、固体潤滑剤として黒鉛を用いるが、締付け締戻し時に、固体潤滑剤としての黒鉛がバインダー樹脂と一体化してしまい、長く展伸してテープ状の2次生成物となることを抑制する成分設計を行う。これによって、焼き付きリスクを下げることが可能となる。
本開示の固体潤滑被膜や薬剤は、実際の井戸で使う環境に即した評価方法で、可否を評価してパラメータの上下限設定する。これによって、潤滑補助若しくは軽度焼き付き部分を補修できる、実際の井戸での使用に耐える薬剤及び固体潤滑被膜を提供する。
(1)石油/ガス掘削関係者の間では、メカニズムはどうであるにせよ、MoS2は、結果としてH2Sになるとか、水素脆化割れを引き起こす懸念が高いという考えが根強くある。非特許文献1で報告されているような、認知されている危険因子を避けるためには、MoS2を使わない成分系対応とする必要がある。そして、本開示では、次のようなスプレー、ペースト、液体状の潤滑スプレー、潤滑塗料は、使用しない。つまり、広く普及しているモリコートや、その類似商品のような、MoS2を主成分として含む。そして、PTFE、黒鉛、BN、シリコン等の固体潤滑剤を状況に応じて添加する。更に溶剤に、鉱物油系~合成油系(ホワイト・ミネラル・オイル、PAO、PAG等)に展開させたスプレー等は、本開示では使用しない。
同時に、井戸元タッチアップ(固体潤滑被膜の部分補修)、及び、油井管ねじの潤滑性能の一段階改善を実現させるため、代替材料を使って同等~同等以上の性能がでるように成分設計する。
井戸元のような火気厳禁な場所であっても塗れることも必要である。しかしながら、早期乾燥させるがために、水溶媒に対して、特定化学物質に属するような、揮発性有機溶媒のトルエン、キシレン、ベンゼン等のVOC(揮発性有機溶剤)は使用できない。このため、早期乾燥を実現するために、なんらかの工夫が必要である。特定化学物質は、例えば、米国ならばOSHA、米国労働安全衛生局のルールならば、作業環境測定対象物質に対応する。
よって、本開示では、フッ素系やシンナー系のVOC(揮発性有機物質)以外の方法で、塗ったはなから乾いてしまうような速乾にはできない。しかし、水系で到達しうる目標として、室温放置くらいの環境で30分以内、できれば、15分以内、更に望ましくは5分以内に乾燥できる程度の、早期乾燥性能を持たせる。
特に金属石鹸は、水に不溶であり、アルコールに不溶であるといわれている。このため、金属石鹸を水系ポリマーの原液に均質に近い状態で混ぜることには、工夫が必要である。
同じく、黒鉛は、それ自体だけを使った潤滑剤を活用される際には、水系ソリュブルや油などの溶媒に添加物等を適宜入れて、混合分散したものが使われている。したがって、単なる水を主体とする溶剤に均質分散して薬剤設計するのには、金属石鹸同様に、水系溶剤に溶けるように、同じく工夫が必要である。
特許文献5~7は、シンナー系のVOCに混ぜて、これらの揮発性を活用して水系溶剤の揮発を促進した例である。しかし、本開示では、最も厳しい利用条件では、井戸元での火気厳禁環境での利用が可能であることを目指すため、これらの発想に基づいた方法の、シンナー系の有機溶剤は使うことを想定しない。
また、タッチアップときには、グラインダーやペーパーで養生したあとに、本開示の薬剤を塗布する。このとき、固体潤滑被膜がなくなってしまっていたり、一部欠損していたり、ねじ部分の金属も削られてなくなってしまっている場合もある。黒鉛によって、その削られた補修部分を埋めることと、潤滑を達成することと、長く展伸してテープ状の2次生成物を作らないことを達成する工夫を行う。すなわち、約30mmを超えるような長いテープ状のようなものを作らないようにする。また、テープ状であっても短く、断片的で、可能なら、粉末状の状態で、黒鉛が点在するようにする。つまり、黒鉛からなる固体潤滑剤が、ボックスねじ、ピンねじに一様に転写されるようにする。すなわち、テープ状の2次生成物を作らず、固体潤滑被膜由来の粉状又は小さな破片状のものか、これらの2次生成物が、締付け締戻しに連動して動くようにして、ねじ間隙に詰まらないようにする。この状態を、固体潤滑剤に黒鉛を選択した際でも、安定して達成しうるようにする。
また、市販の潤滑スプレーのように、バインダー樹脂がなくて、潤滑剤だけが最表層に置かれた状況になる従来技術も、本開示とは発想が異なる。本開示は、軟質なバインダー樹脂がある中で、その膜の中に固体潤滑剤が取り込まれる。それと共に、バインダー樹脂の外に、更に別種の固体潤滑膜も存在する状況をも含んでいる。これは、従来の潤滑スプレー等とは、技術発想が異なるものである。
これは、過去の先行文献に共通して言えることである。規定範囲に意味を持たせるためには、潤滑性の評価を、実井戸での締付け締戻しか、模擬井戸か、それに即したシミュレーションができている新たな評価手法で評価する必要がある。
また、本開示は、例えば、油井管ねじ継手の潤滑で、油井管ねじの構成要素(ねじ部)における、ねじ山部分とシール部分のうち、ねじ山部分だけに軽度な焼き付きが起きた場合の補修技術である。すなわち、本開示は、井戸元でのリペアに用いる補修技術である。焼き付き部分を、グラインダー、サンドペーパー、やすり等で削って養生する。その後に、養生部分を含めて、その領域にタッチアップの目的で、本開示の薬剤を塗布することで補修する。更に、本開示は、薬剤が膜化した状態での油井管ねじ継手に関する。
更に、本開示は、固体潤滑被膜の更に1段階レベルアップした潤滑性が必要な場合に、潤滑性の向上を目的とする。又は、予防的な意味を含めて焼き付きを避けることを目的とする。本開示は、そのような目的のために、本来ある固体潤滑被膜の上に塗布してトップコートを形成する技術も含む。
これが成立するために、本開示では、コーティング用薬剤中で、金属石鹸を均質に混ぜ込むことを前提にしている。すなわち、元々、撥水性があり水に不溶な金属石鹸を、均質的にうまく調合することを前提としている。
また、用途からして、早期乾燥性が求められるが、井戸元での火気厳禁環境でも使えるように薬剤の調合を行う。
これらの個々の条件を満足させるよう配慮することによって、本開示で規定する範囲内で良好なタッチアップ的な部分補修時の潤滑、及び、固体潤滑被膜の1段階上の潤滑性アップを図ることができる。本開示は、前項で述べた課題を解決するために、以下の新たな解決手段を用いて、発明を構成するものである。
薬剤にMoS2を含まないように設計し、乾いた後の膜にもMoS2を含まないように設計する。
また、これらの市販の潤滑剤が使っている、鉱物油系~合成油系のホワイト・ミネラル・オイル、PAO(ポリ‐α‐オレフィン)、PAG(ポリアルキレングリコール)等を、溶媒として使わないようにする。本開示では、MoS2ではなく、まったく技術系統が異なる、黒鉛と金属石鹸を潤滑剤として使う。
従来、金属石鹸は、油に添加して、粘度を上げる添加物として使われることが多い。本開示では、金属石鹸を、増粘剤、増稠剤として使用しない。本開示では、金属石鹸を、油系の溶剤の粘度を上げるために添加するのではない。本開示では、金属石鹸には、潤滑剤の役割と、早期乾燥するための1つの手段としての役割がある。しかも、本開示は、撥水性を有する金属石鹸を、水主体の溶剤に分散させて用いることにも特徴の一つがある。
さらに、更なる溶剤の構成分の添加物として、アンモニア水を添加してもよい。28-30%アンモニア水は、いわゆる、濃アンモニア水として本開示は規定している。しかし、薄いアンモニア水を使う場合には、濃度に応じて割り戻した数値として読み替えるものとする。
バインダー樹脂は、水溶性若しくは水分散性のポリマーである。バインダー樹脂は、全バインダー樹脂重量を分母としたときに、アクリレート、メタクリレートに属するモノマーを90%以上含む、ポリマーか共重合体である、コーティング用薬剤の組成にした。
水を主体とした溶剤にした理由は、作業者の安全を担保し、火気厳禁でも使用出来、且つ有害成分を含まないことを狙ったためである。
なお、上記に次のことを記載した。その記載とは、「全溶剤中で、水と低級アルコールの合計体積が95%以上」とか、「固体潤滑剤は黒鉛と金属石鹸の合計が95%以上」とか、「バインダー樹脂はアクリレート、メタクリレート系が90%以上と」とかである。これらの記載は、不純物とか微量添加物、又は、意図的な添加ではないものが混じった場合でも、ここで表記されるレベル程度ならば許容され、特性に影響を与えないという意味である。
更に、早期乾燥性を促進させるための好適範囲として、固体潤滑剤のサイズを、金属石鹸及び黒鉛共に、平均粒径が5μm以下になるように規定した。更に本開示では、金属石鹸及び黒鉛の添加量を最適化して、早期乾燥を実現させる。
固体潤滑剤の粒径を小さくするのは、まだ乾いていないコーティング用薬剤の早期乾燥を促すために、表面積を増やすものを入れ込んでおくという発想である。更に、微小サイズの固体潤滑剤は、潤滑に効果的であるからである。早期乾燥及び潤滑の両方の観点から、固体潤滑剤の粒径は5μm以下が好ましく、小さいほどよい。望ましくは、金属石鹸及び黒鉛共に、粒径が1μm以下である。
この好適範囲が設定される理由は、次の通りである。薬剤が薄い状況、つまり、溶剤が多い状況は許容できるが、粘性が下がり、粘性が低くなり、薬剤の流動性が高くなる。同時に水成分が多くなるので乾燥時間がかかる。薬剤が薄いがために、何重も重ねて塗布して、乾燥もその都度くり返すことをすれば、その薬剤が資料できることは可能にはなり、潤滑・防錆特性は確保される。しかし、使い勝手が悪く、現実的とは言い難い。
金属石鹸は、潤滑にとって有効に機能する。しかし、金属石鹸は、火気厳禁環境での使用を想定すると、アルコールを使っての金属石鹸の事前溶解にも限界がある。金属石鹸を、水系ポリマーから構成されるコーティング用薬剤に均質に混ぜるために、金属石鹸の添加量が限定されてしまう。このため、上限の5%が決まってしまう。また、下限0.5%以上というのは、微細な黒鉛との相乗効果で、早期乾燥が達成されうるための必要量であることから決まり、潤滑特性も同時に実現するために規定した。
コーティング用薬剤には、金属石鹸や黒鉛が、均質に混じっていることが前提である。
しかしながら、金属石鹸は、油には溶けるが、撥水性を有し水に不溶であるといわれている。このため、金属石鹸は、普通であれば、本開示の水主体の溶媒にはうまく混濁させることができない。したがって、工夫が必要である。同じく、黒鉛も、原則、水に不溶である。従来、それ自体だけを潤滑剤として活用する場合、油やソリュブルなどの溶媒に添加物等を、適宜入れて、混合分散したものが使われている。そのまま、工夫もなく、黒鉛を水系溶剤に溶解すると、黒鉛は表面に浮いてしまう感じになる傾向になる。黒鉛をできる限り分散させることが、黒鉛が、固体潤滑剤として活用する点では好ましい。
金属石鹸については、本発明者らは、水に不溶とされる金属石鹸を、水溶性若しくは水分散性のポリマー(水系ポリマー)の溶剤である水に、溶剤へ添加する溶剤補助成分を混ぜるラボ検討実験を行う中で、次の知見を得た。
すなわち、金属石鹸は、水にもエタノールにも不溶とされる。しかし、実際に溶かしてみると、水と、エタノールをはじめとする低級アルコール群を比較したときに、金属石鹸の分散溶解挙動が異なることを観察する中で気付いた。エタノールをはじめとする低級アルコール群では、金属石鹸はダマになりづらく、微粒子化しやすい傾向があり、金属石鹸を微粒子のまま保つことができる。金属石鹸をアルコールに混ぜてから、強撹拌したり超音波で振動を加えたりしてもよい。一方で、水だけでは、金属石鹸が会合して大きくなってダマになり、均質な分散状態になりえない。
ここで、このコーティング用薬剤は、静置しておくと、時間が経過するほど、金属石鹸が分離してくる。しかし、薬剤を収容した容器を振る等して再度混濁させてから塗布した場合、溶剤の水を飛ばす、つまり蒸発・揮発させることで、均質な固体潤滑被膜になることが確認できた。
なお、直接、水に溶かした場合には、金属石鹸がダマになる傾向があるため、固体潤滑被膜になったときに、不均質な膜になる懸念が高くなってしまう。
黒鉛についても、金属石鹸の水系溶剤への溶かし込みと同じように、低級アルコールを活用することができる。ただし、本開示のような低級アルコールが、水100に対して10以下のような状況では、金属石鹸ほどには溶かし込むことが難しい。この場合、一部、溶剤表面に浮いている場合も含むが、大方の黒鉛は分散しているか、もしくは、塗布前に薬剤全体を振る等して一様分散するように工夫して使うとよい。
後述する潤滑挙動を改善させる点では、アルカリ石鹸は含有させたほうがよい。アルカリ石鹸は、水に可溶なので、水主体の溶剤に溶かす観点では、特に問題はない。本開示では1%を上限にして溶解してもよい。1%以上の溶解は、薬剤全体の粘性を上げてしまって均質塗布が困難になるので、よくない。
ここで目指すべき、引火点は不燃と評価される状態が最も好ましい。しかし、薬剤の引火点が60℃以上の環境であれば、井戸元の環境での火気厳禁の環境ならば利用可能に思われる。したがって、そのレベルまでの低級アルコールの利用は許容できる。なお、アンモニアの揮発も活用してもよい。アンモニア水は、引火点が不燃の扱いである、また、アンモニア水は、コーティング用薬剤を構成するアクリル系バインダー樹脂のpH調整にも使われる。このため、pH調整範囲での上限に近い領域になるようにアンモニア水を使ってpHを上げて、その揮発性を活用することを併用すると好ましい。
単なる黒鉛だけではなくて、黒鉛がバインダー樹脂成分と一緒になった膜の状態では、黒鉛は、ねじ溝に沿って拘束されている。それと同時に、黒鉛がバインダー樹脂と一体化することも影響して、テープ状(カセットテープのような状態)の2次生成物ができやすくなる。これらは、ねじの締付け締戻しに連動して動きづらい。この結果、ねじ間隙に詰まりやすくなり、結果として焼き付きの原因になってしまう公算が高くなる。よって、黒鉛が粉末状や破片状で、テープ状にならないように成分設計するように図る必要がある。
固体潤滑被膜構造が、黒鉛+金属石鹸が膜中に完全に取り込まれる状況から、黒鉛単体が、固体潤滑被膜の最表面にも付着するような感じで存在するくらいに分布するくらいの場合を含む。そして、黒鉛総量が、全固体潤滑剤(アルカリ石鹸含有量込みとする)に対して、上限5%以下にすることが必要である。
更に好適な範囲は、1%以上3%以下が好ましい。下限を1%以上、かつ、上限を3%以下の方が、この順で、一層黒鉛による潤滑改善効果を期待でき、かつ、テープ構造の2次生成物の形成が一層回避されやすくなる。
黒鉛の添加が原因となって、テープ状の2次生成物が、ねじの締付け締戻し時に形成されてしまって、焼き付きをもたらすことを避ける必要がある。
上記の範囲限定をした時に、黒鉛由来のテープ状の2次生成物が出来にくくなる理由は、以下のように考えらえる。
同時に、金属石鹸、黒鉛共に、微細な構造体であることで、溶剤との接触面積が増えることで乾燥ポイントが増える。したがって、サイズが5μm以下であることによって、早期乾燥を図ることにも貢献している。
その際、黒鉛の添加量によっては、黒鉛がむしろ逆に、ねじ溝に沿ってテープ状構造を作ってしまって、焼き付きの原因にならないように工夫する必要がある。
金属石鹸及び黒鉛は、2つの寄与がある。すなわち、それら固体潤滑剤が、膜から離れて、それぞれが単独及び複合的に潤滑に寄与する部分と、バインダー樹脂と一体となった2次生成物として、潤滑に寄与する分がある。
グラインダーやペーパーで養生ししたあとに、本開示の薬剤を塗布して、ねじ焼き付き時の軽度焼き付き等を補修する。
このとき、養生後の状態において、固体潤滑被膜がなくなってしまっていたり、固体潤滑被膜が一部欠損していたり、ねじ部分の金属も削られてなくなってしまっている場合もある。例えば、1~2mmオーダーの厚みがなくなっている場合もありうる。そのため、まずその部分を埋める目的を達成するために、本開示では、上述の成分規定を同じではあるが、水系ポリマー(アクリル系)と、固体潤滑剤と、水の重量の配合規定を、全構成成分の重量に対して、それぞれ下限値として次のように設定した。すなわち、それぞれの下限値として、30%以上、10%以上、40%以上とした。また、それぞれの上限値として、40%以下、20%以下、50%以下にした。
また、本開示の固体潤滑被膜、コーティング用薬剤は、実際の井戸で使う環境に即した評価方法で、可否を評価し、パラメータの上下限を規定した。これによって、実際の井戸でも使用が耐えるような、潤滑補助若しくは軽度焼き付き部分を補修が可能となる。
その評価方法は、短尺ピンの上端部に、実長ピン1本~3本程度の重錘をつける。更に、ねじの初期セット位置を、ピンねじ山がボックスねじに対して半分程度露出する状態とする。そして、締付けときには重錘を印加し、締め戻しときには重錘を印加しないようにして、実際の井戸での締付けを模擬する。装置例を図6及び図7に示す。その構成例については、後述する。
本開示では、この新たな装置構成での評価に基づきパラメータを規定して、実際の井戸でも使用が耐えるような潤滑性能を担保した。
(構成)
<薬剤>
本実施形態の薬剤は、油井管などの金属部品の金属面に対し潤滑性能を付与するための薬剤である。薬剤は、固体潤滑剤と、バインダー樹脂と、溶剤成分とを主成分とする。主成分とは、例えば、残部が不可避的に入る材料であったり、固体潤滑剤とバインダー樹脂と溶剤成分とで全重量の95%以上の場合を指す。
溶剤成分は、水を主成分とし、その水に対し炭素数3以下の低級アルコールが添加物として添加される。
添加物の水に対する体積は、水の体積100に対し10以下である。
溶剤の体積の95%以上が、上記水と上記添加物で構成される。
上記添加物として、更にアンモニア水が添加されていても良い。
溶剤は、例えば、薬剤全重量の40%以上50%以下であることが好ましい。
溶剤は、例えば、炭素数3以下の低級アルコール及びアンモニア水のうち、少なくとも炭素数3以下の低級アルコールが添加されている。
その炭素数3以下の低級アルコールの体積は、溶剤を構成する水の体積100に対し0.5以上10以下とする。アンモニア水の体積は、溶剤を構成する水の体積100に対し0以上5以下とする。
炭素数3以下の低級アルコールとしては、メタノール、エタノール、イソプロピルアルコール、ノルマルプロピルアルコール、工業用エタノールから1又は2以上選択した低級アルコールが例示できる。
固体潤滑剤として、黒鉛と金属石鹸を含む。その黒鉛と金属石鹸が、全固体潤滑成分重量の95%以上である。
固体潤滑剤は、例えば、薬剤全重量の10%以上20%以下が好ましい。固体潤滑剤の主成分は金属石鹸である。すなわち、金属石鹸は、重量比で、黒鉛よりも多く含有させる。
黒鉛は、例えば、重量比で、全固体潤滑剤の0.5%以上5%以下とする。更に好適な範囲は、1%以上3%以下が好ましい。下限を1%以上、かつ、上限を3%以下の方が、一層黒鉛による潤滑改善効果を期待でき、かつ、テープ構造の2次生成物の形成が一層回避されやすくなる。
また、好適な範囲として、金属石鹸、黒鉛の粒径は、共に、例えば5μm以下が好ましい。理由は、すでに述べているように、固体潤滑被膜が、締付締戻し時にダメージを受けやすくなることを回避するためと、微細サイズにすることで早期乾燥に一助にするためである。
A群:ステアリン酸、ベヘン酸、ラウリン酸、12-ヒドロキシステアリン酸、オレイン酸、モンタン酸
B群:Mg、Ca、Zn、Ba
C群:Na、K
バインダー樹脂は、水溶性若しくは水分散性のポリマーである。そのポリマーは、アクリレート、メタクリレートに属するモノマーを全バインダー樹脂重量の90%以上含むポリマーか共重合体である。
バインダー樹脂は、例えば、薬剤全重量の30%以上40%以下とする。
バインダー樹脂を構成する水溶性若しくは水分散性のポリマーは、例えば、(1)~(4)に記載のモノマーのうち、単体で構成されるポリマーか、2個以上のモノマーならなる共重合体である。
(2)アクリレート、メタクリレート、及び、これらの個々の誘導体に、アルキルエステル、ビニルエステル、スチレンエステル、カルボン酸エステル、及び、これらの個々の誘導体を含んだモノマーと一体となったモノマー
(3)上記(1)(2)に対してグラフト化したモノマー
(4)ビニル化合物、ウレタン化合物のうちのいずれか一方か両方のモノマーが、少なくとも(1)~(3)のうちの1つ以上のモノマーと一体となって構成されるモノマー
薬剤は、薬剤の粘度が、1000mPa・sec以下である。
薬剤は、金属面に対し、塗布量1mg/mm2以下で塗布した場合、常温の無風の大気環境で放置乾燥をした場合、30分以内に乾燥可能な早期乾燥性を有する。ただし、大気で常温乾燥とは、常温(15-30℃、例えば24℃)での乾燥を意味する。
薬剤は、低級アルコールに金属石鹸を分散混濁させたあと、溶剤の水へ投入することによって、金属石鹸の調合を行う。
油井管のねじ部の潤滑膜を補修する油井管補修方法である。
油井管のねじ部のうち、焼き付きが発生した領域を養生したのちに、少なくとも上記養生部分に対し、本開示のコーティング用薬剤を塗布する。これによって、削れた領域を、黒鉛を含む膜で埋めて補修できる。
ねじ部に形成された油井管に形成れている既存の潤滑被膜の上に、本開示のコーティング用薬剤を塗布する。これによって、潤滑性能の向上を図る。
油井管は、図1に示すような、雌ねじ2aを有するボックス2や、雄ねじ1aを有するピン1である。
油井管ねじ継手は、図1に示すように、雌ねじ2aを有するカップリングなどのボックス2と、雄ねじ1aを有するピン1とからなる。そして、ボックス2及びピン1のうちの少なくとも一方の部品における、ねじ部の接触面(締結面10)に、本開示の固体潤滑被膜を備える潤滑被膜が形成されている。
固体潤滑被膜は、バインダー樹脂と、バインダー樹脂中分散した固体潤滑剤とを有する。
固体潤滑被膜は、マトリック成分としてのバインダー樹脂に固体潤滑剤が分散している。
固体潤滑剤として、黒鉛と金属石鹸を含み、その黒鉛と金属石鹸が、全固体潤滑成分重量の95%以上である。
金属石鹸は、例えば、重量比で、全固体潤滑剤の0.5%以上5%以下とする。
金属石鹸は、例えば、次のA群から選択した脂肪酸とB群から選択した金属元素(金属イオン)からなる化合物からなる、1種類若しくは2種類以上の金属石鹸からなる。
アルカリ石鹸は、例えば、次のA群から選択した脂肪酸とC群から選択した金属元素(金属イオン)からなる化合物からなる、1種類若しくは2種類以上のアルカリ石鹸からなる。
B群:Mg、Ca、Zn、Ba
C群:Na、K
バインダー樹脂を構成する水溶性若しくは水分散性のポリマーは、(1)~(4)に記載のモノマーのうち、単体で構成されるポリマーか、2個以上のモノマーならなる共重合体である。
(2)アクリレート、メタクリレート、及び、これらの個々の誘導体に、アルキルエステル、ビニルエステル、スチレンエステル、カルボン酸エステル、及び、これらの個々の誘導体を含んだモノマーと一体となったモノマー
(3)上記(1)(2)に対してグラフト化したモノマー
(4)ビニル化合物、ウレタン化合物のうち、いずれか一方か両方のモノマーが、少なくとも(1)~(3)のうち、1つ以上のモノマーと一体となって構成されるモノマー
なお、固体潤滑被膜の下層に下地膜(不図示)、例えば、リン酸Mn化成処理膜、電気めっき膜等を有していても良い。
ボックス及び上記ピンのうちの一方の油井管を、本開示の潤滑被膜が形成された油井管とする場合、他方の油井管のねじ部には、上記固体潤滑被膜より硬度が高い被膜が形成されていることが好ましい。
以上のように、本開示の薬剤は、水溶性若しくは水分散性のポリマー(水系ポリマー)をバインダー樹脂とし、固体潤滑剤を金属石鹸と黒鉛の混合系にして、溶剤を水にした主成分系のコーティング用薬剤から構成させたコーティング用薬剤である。
また、例えば、ねじ山部分やシール部分で構成されるねじのうち、ねじ山部分だけに軽度な焼き付きが起きた場合に使用する。つまり、井戸元で行うタッチアップ的な部分補修時に、本開示の薬剤を、養生後に補修する表面に塗る。これによって、本開示の油井管や油井管ねじ継手が構成される。
まず、目標とする必要特性について述べて、そのあとに、個々のパラメータの規定範囲と、その意味を説明する。
なお、本開示は、潤滑補助と、タッチアップ的な部分補修時の潤滑を意図している。このため、耐食性は特には意図しない。耐食性は、既にある固体潤滑被膜で達成するものであり、かつ、タッチアップ的な井戸元での部分補修では、補修後にはすぐに締付けが行わるので、潤滑のみを対象にしたものである。
本開示が意図する、油井管ねじの固体潤滑被膜として活用時には、固体潤滑被膜の潤滑特性を元にして判断しつつも、固体潤滑被膜特有である、徐々に膜が消耗していることを鑑みる。そして、API-5C5やISO13679の規定等とは若干異なる基準で潤滑性能を判断する。ケーシングサイズは締付け締戻し回数が2回以上、チュービングサイズは締付け締戻し回数が5回以上を合格判定基準とした。上述してきたように、その特性の確認については、実井戸を模擬出来るような新たな評価方法で確認することを前提とする。
補修は、グラインダー、やすり、ペーパー等を使って焼き付き部分を養生したあと、潤滑を再度確保するために実行される。具体的には、焼き付き箇所を含んで、その周りだけか、若しくは、全面に本開示の薬剤を塗布して行う。
焼き付いた状態から更に1回以上締め付けが増加することができれば、良好(合格)とみなす。更に、そのまま1回以上(計2回以上)、締付け締戻しできれば、更に良好とみなす。この軽度の焼き付き部分の補修の評価についても、その評価方法は、上述した、実井戸を模擬出来る新たな評価方法で確認することを前提とする。
この模擬では、実井戸模擬での締付け締戻しを1回した後に、物理的ダメージを与えて、その部分をグラインダー、ヤスリ、サンドペーパー等で養生した状況を意図的に作る。その後に、本開示の薬剤を塗布してタッチアップ補修する。
本開示は、水系溶剤を採用するが、次のことで、塗布した薬剤の早期乾燥化を図ることを意図している。すなわち、低級アルコールやアンモニアの揮発性の活用と、金属石鹸と黒鉛についての調合範囲の設定及びサイズ管理を行う。更には、金属石鹸と黒鉛がダマにならない工夫をする。更にまた、固体潤滑剤のバインダー樹脂への取り込み方法を変える等を行う。
早期乾燥のレベルについては、2つの基準をもって判断する。
1つ目の基準は、上記のような工夫をしない時と比べて、早く乾燥できることを達成可能か否かの基準である。大気放置なら大気放置同士の比較をし、送風乾燥なら送風乾燥同士で比較をした際に、早期に乾燥することを目標とする。比較する場所・位置も同等な位置で評価する。
具体的には、金属面に塗布量0.1g/mm2以下としたときに、大気放置乾燥をしたときに、常温において、30分以内に乾燥できる適度の早期乾燥性を持つことが好ましい。この早期乾燥性は、下記の詳細説明も含め、本開示で規定されたパラメータ群によって、達成しうるレベルである。これができれば、送風乾燥や、温風乾燥では、より早期に乾燥が可能になる。
これらの評価位置は、水系アクリル系バインダー樹脂ベースの水系塗料を、油井管ねじを横に寝かせて塗った場合には、ねじ溝に沿って、液が垂れていき、6時位置で溜る傾向がある。このため、その部分の乾きが若干遅くなる傾向があるので、比較評価する場所は、9時から3時位置での乾燥の比較とする。油井管ねじを立てて塗った場合には、ピンねじの場合には、そのまま垂れたものは、地面に落ちるので特に溜るところはない。しかし、ピン先端で水滴状の垂れが形成される場合がある。その場合、その部分を除外して乾燥時間を評価する。ボックスねじの場合には、同じく、下方向に垂れていく。しかし、プレミアム・ジョイントの場合、ショルダー部分段差に溜る傾向はゼロとは言えず、その部分を除外して乾燥時間を議論する。
早期乾燥性が必要な理由は、このコーティング用薬剤、それを使った固体潤滑被膜が、もっとも厳しい条件として、井戸元で軽度な焼き付き他のトラブルで、タッチアップ的な補修作業に使うことを想定しているからである。そのため、やすりや、研磨ペーパー他で問題個所を削って手直ししてから、本開示のコーティング用薬剤で補修を行うことを意図しているからである。コーティング用薬剤補修とは、補修部分を埋める、潤滑の確保ことを指す。そのため、火気厳禁で使える前提や、乾燥に関わるユーティリティが使えないことも想定して、大気での放置乾燥、送風による乾燥での、早期乾燥を意図した。
本開示は、水系溶剤を使って、次のような工夫で早期に乾燥を図る。すなわち、低級アルコールやアンモニアの揮発性を活用する。また、金属石鹸と黒鉛についての調合範囲の設定及びサイズ管理を行う。更には、金属石鹸と黒鉛がダマにならない工夫、及び、固体潤滑剤のバインダー樹脂への取り込み方法を変える等を行う。これらで早期に乾燥を図る。
詳細は、下記で、個々の項目ごとに説明するが、全体の概要について、コーティング用薬剤の設計思想について述べる。
本開示の薬剤は、低級アルコールを含む。
低級アルコールの含有については、火気厳禁な環境でも使えることを意図するため、薬剤の引火点が60℃以上か、不燃と見なせるように濃度調整する。そして、低級アルコールの揮発性を活用して、早期乾燥を図る。
状況により、薬剤には、アンモニア水の揮発性も併せて活用し、ドラフト設備を使用せずに使うことができるレベルで、これらの濃度を適切な範囲に制御する。
また、含有する金属石鹸や黒鉛の濃度と粒径を、適切な範囲に制御して、早期乾燥を実現させる。具体的には、平均粒径が小さいサイズを選び、また、その濃度を適切な量にする。これによって、固体潤滑剤の表面積総量を稼いで、低級アルコールとアンモニアの揮発を活用して、早期に膜化を図る。
また、固体潤滑剤の溶かし込みでは、金属石鹸自体や黒鉛自体で会合することでダマになってしまい、見かけの大きさが、個々のサイズを超えて大きくなってしまわないように工夫が必要である。このダマの形成回避のため、金属石鹸および黒鉛では、金属石鹸を低級アルコールと一旦は溶解させたうえで、水からなる溶剤や水系ポリマーの混合液へ混ぜることで実現を図る。
コーティング用薬剤の粘度を、1000mPa・sec以下に調合することで、薬剤が厚く塗れないように薬剤を調合する。要は、薬剤として、粘度が低く、サラサラの液粘度にすることを意図する。粘度の下限は、設定しないが、おおよそ40mPa・sec以上にはなる。水溶性若しくは水分散性のポリマー材料を入れて、水溶剤に調合した際には、水の粘度である1mPa・secにはなるはずはなく、粘度の高いものになる。この結果、そのレベルがおおよそ40mPa・sec以上ということになる。
薬剤は、固体潤滑剤とバインダー樹脂と、薬剤塗布後に被膜に残存しない溶剤から主に構成される。
溶剤は、水主体である。その水に対し、1又は2種類以上の、炭素数3以下の低級アルコールを添加物として更に添加した。状況に応じて、上記添加物としてアンモニア水も添加してもよい。
その添加物は、水の体積100に対し10以下とする。また、水と上記添加物の合計体積は、全溶剤体積の95%(vol/vol%)以上とする。
バインダー樹脂は、水溶性若しくは水分散性のポリマーを主成分とする。そのポリマーは、アクリレート、メタクリレートに属するモノマーから構成されるポリマーや共重合体が、全バインダー樹脂成分の重量の90%以上となっている。
以上のように、本開示は、基本組成が、水主体の溶剤、黒鉛+金属石鹸を主体とする固体潤滑剤、アクリレート、メタクリレートに属するモノマーから構成されるポリマー及びその共重合体が主体であるバインダー樹脂からなる。それぞれ、主体というのは、個々の構成要素単位で、95%以上、95%以上、90%以上を指す。要は、僅かな不純物、不可避混合物、鼻薬の混入ならば許容できるという意味である。
アクリレート、メタクリレートに属するモノマーから構成されるポリマーは、それ自体は乾いた膜(マトリクス)になる。膜は、その膜(マトリクス)の中に、金属石鹸と黒鉛の固体潤滑剤を均質的に保持した膜である。固体潤滑剤の一部は、膜(マトリクス)の表層に付着している状況とか、一部を膜(マトリクス)に埋め込まれながら、一部が表面に露出した状態となっている。
なお、低級アルコールやアンモニアの活用は、金属石鹸の均質的な溶かしこみと、揮発性を活用した膜の早期乾燥のために入れたものである。下記で再度詳細に説明する。
本開示では、バインダー樹脂、固体潤滑剤、水の調合割合が、バインダー樹脂(水溶性若しくは水分散性のポリマー)、固体潤滑剤(金属石鹸と黒鉛)、溶剤としての水主体の溶剤が、それぞれ下限値として次の値が好ましい。すなわち、それぞれ30%以上、10%以上、40%以上が好ましい。また、それぞれの上限値として、40%以下、20%以下、50%以下に調合することが好ましい。なお、全体として、これらが100%になるようにコーティング用薬剤を調合する。
水は、環境についての問題が一切ない。この理由から、溶剤の主成分に水を選定する。その溶剤としての水は、膜化したときには、揮発・蒸発して膜から抜け出ていくものである。
膜の早期乾燥性を図るために、水が少ない方が乾燥しやすいと考えがちである。しかし、実際にはそうではない。水が少なく粘性が高すぎる場合には、むしろ乾きにくい場合が多い。
そのため、詳細は後述するが、コーティング用薬剤の粘度を低くして、流動性のよいものにして、薄く塗れるように工夫する。そのために、本開示では、粘度を下げるために、上記のように、水を40%以上入れるのが好ましい。
同時に、水の含有量は、水溶性若しくは水分散性のポリマーの必要量を含有させるために十分な量であることを満足した量になっている。水の上限を50%以下にしたのは、それを超えると、バインダー樹脂自体が薄すぎるようになること、及び、粘度が低くなりすぎて、薬剤を必要量だけ塗れないことが起こりうることから規定されるものである。
水溶性若しくは水分散性のポリマーは、水系アクリル系(メタクリル系)樹脂が主体のポリマーを指す。これを、30%以上40%以下に調合させることが好ましい。
固体潤滑剤は、金属石鹸と黒鉛を主成分とし、しかも主体は金属石鹸ではある。すなわち、金属石鹸は黒鉛よりも多く含有させる。
よって、固体潤滑被膜として性質を実現するために、上記の水主体の溶剤に溶け込める前提で、バインダー樹脂と固体潤滑剤の重量比は、バインダー樹脂の重量に対して、固体潤滑剤の重量比が、0.25~0.66の間に位置させて調合することが重要である。更に望ましくは、0.3以上0.5の重量比の範囲が好ましい。この比率のものが結果として、ねじ表面に固体潤滑被膜として形成される。
バインダー樹脂の中に、固体潤滑剤を均質に分散配置するには、潤滑改善につき限界値がある。固体潤滑剤が多すぎると膜内に入りきらずに、表面に付着しただけのものになり、潤滑の改善を十分に実現するには不利になる。よって、好適範囲として上限が0.5になる。逆に少なすぎると、潤滑に必要な固体潤滑剤が少ない状況になり、潤滑目標レベルを維持できない。よって、好適な下限が0.3になる。
水以外の溶剤成分として、1種又は2種類以上の、炭素数3以下の低級アルコールを水の体積100に対し0.5以上10以下添加される。更に、アンモニア水が、水の体積を100に対し0以上5以下添加することができる。
炭素数3以下の低級アルコールは、メタノール、エタノール、イソプロピルアルコール、ノルマルプロピルアルコール、工業用エタノールから選択した1種以上の低級アルコールであることが好ましい。
下記で詳細は述べるが、薬剤の引火点を60℃以上、又は、不燃であるためには、これらの低級アルコールの濃度の上限を制限して、薬剤の引火点を高くように調整する必要がある。
下限(水の体積100に対し0.5以上)の規定は、揮発性の活用を行える最低限を意味する。上限(水の体積100に対し10以下)の規定は、引火点の調整のための許されるうる上限として設定されたものである。
本明細書では、アンモニア水を、濃アンモニア水(28-30%アンモニア含有)として表現している。薄いアンモニアを使う際には、濃アンモニア水の調合割合に、割り戻しして規定されているものとして読み替えることとする。
同時に、低級アルコールは、固体潤滑剤である金属石鹸をダマにすることなく、金属石鹸を添加した際のサイズのまま会合することを避けて、調合する役割がある。
黒鉛の平均粒径を5μm以下、金属石鹸の平均粒径を5μm以下とする。
また、固体潤滑剤のうち、黒鉛の重量比を0.5%以上5%以下とし、残りの主要成分を金属石鹸とする。併せて、上限1%にして、アルカリ石鹸を含有することができる。
本開示では、主に潤滑を金属石鹸で持たせて、黒鉛で更に改善させる。アルカリ石鹸も潤滑改善効果を期待できる。しかし、アルカリ石鹸がもたらす更なる効果として、次の機能がある。すなわち、アルカリ石鹸は、初期のピンねじとボックスねじの噛み合いの位置のズレから、正規な噛み合い位置へ滑り込むように誘導させるのに有効に機能する。アルカリ石鹸は、特に少し湿気がある状況でも効果がある。かつ、アルカリ石鹸は、降雨や、井戸からの逆流があるような状況で、ねじ山が濡れた状況においても、効果的に、正規なねじの噛み合い位置へ滑らせる効果がある。
黒鉛と金属石鹸の粒径は小さいほどよい。好ましくは1μm以下のサイズである。5μmを超えた場合には、固体潤滑被膜になった際の膜厚と同じレベルの固体潤滑剤が出てくる状況になる。また、膜厚内に埋め込まれない場合には、膜が、油井管ねじの締付け締戻し時に、容易に破壊することにもつながる場合もある。この観点から、5μm以下である必要がある。本開示では、後述するが、膜厚は10μm以上100μm以下が好ましい範囲として規定する。黒鉛と金属石鹸の粒径が5μm以下、望ましくは、1μm以下の粒径であれば、油井管ねじの締付け締戻し時に、膜が容易に破壊される懸念も小さくすることができる。
テープ状2次生成物は黒鉛の添加に伴い締付け締戻し時に形成される傾向が高い。そのテープ状2次生成物の根源は、ねじ溝に沿って伸びた黒鉛が主体になって形成された構造体である。黒鉛の添加による潤滑向上効果を打ち消すように、黒鉛によるテープ状の2次生成物が長く形成されてしまって、ねじ間隙のどこかで詰まってしまう時には、焼き付きが発生する懸念が高くなる。
黒鉛がバインダー樹脂に分散されているために、構造的にテープ状の2次生成物を作る傾向は否定できない。しかし、テープ状を、剥離片状、破片状、粉状的に変化させることで、焼き付きを回避する。
また、金属石鹸のサイズ規定として5μm以下が好ましい理由も、黒鉛と同じように、固体潤滑被膜自体の破壊されやすくなることを避ける意味合いがある。
同時に、金属石鹸、黒鉛共に、微細な構造体であることで、溶剤との接触面積が増えることで乾燥ポイントが増えるの。このため、5μm以下であることによって、早期乾燥を図ることにも貢献している。
バインダー樹脂を構成する水溶性若しくは水分散性のポリマーについては、下記(1)~(4)のモノマー単体で構成されるポリマーか、2個以上のモノマーならなる共重合体であることが好ましい。
(2)アクリレート、メタクリレート、及び、これらの個々の誘導体に、アルキルエステル、ビニルエステル、スチレンエステル、カルボン酸エステル、及び、これらの個々の誘導体を含んだモノマーと一体になったモノマー
(3)上記(1)(2)に対してグラフト化したモノマー
(4)ビニル化合物、ウレタン化合物のうちのいずれか一方か両方のモノマーが、少なくとも(1)~(3)のうちの1つ以上のモノマーと一体になって構成されるモノマー
本開示の薬剤では、水がほとんどを占める溶剤の中にバインダー樹脂が溶けている。そして、これを塗布し、水を飛ばして、つまり蒸発・揮発させて膜化する。なお、環境に配慮するという基本方針がある。このため、昨今問題視されるようになってきた、鉛をはじめとする重金属類、及び、PFASと呼ばれる群のフッ素を含むアルキル基を含有する素材を使わずに設計する。
金属石鹸、および、アルカリ石鹸は、1種類若しくは2種類以上の高級脂肪酸と、金属元素(金属イオン)の組み合わせからなる。その各金属石鹸は、下記のA群から選択した脂肪酸とB群から選択した金属元素(金属イオン)からなる化合物であることが好ましい。各アルカリ石鹸は、A群から選択した脂肪酸とC群から選択した金属元素(金属イオン)からなる化合物であることが好ましい。
・A群:ステアリン酸、ベヘン酸、ラウリン酸、12-ヒドロキシステアリン酸、オレイン酸、モンタン酸
・B群:Mg、Ca、Zn、Ba、Al
・C群:Na、K
油井管ねじの潤滑で、潤滑状況がよくないものでは、潤滑部分が熱を発することがあるので、形成した固体潤滑被膜の融点は高いものが好ましい。固体潤滑被膜の融点は、100℃以上の融点であることが好ましく、上記の好ましい事例は、この条件をクリアできている。
薬剤の引火点が60℃以上であることか、好ましくは引火点が150℃、引火点が測定することができず不燃扱いであることが好ましい。
井戸元でタッチアップ的補修を想定したときに、火気厳禁の環境で使う場合が想定されうる。まずは、塗布する環境温度として、-50~+50℃くらいを想定する。余裕を見て、-60~+60℃で使うことを想定しうる。また、現状の井戸底の温度でもっとも高い温度として、例外的に250℃、伝熱して井戸元の温度でありうる最も高めに想定できる温度として150℃が想定される場合がある。このため、上記のように、温度範囲を設定した。危険度ゼロにするには、引火点が測定できず、不燃として分類されるようにすることである。これは、低級アルコールの選択と、その調合割合によって調整することができる。
コーティング用薬剤の粘度が、1000mPa・sec以下であることが好ましい。
薬剤の粘度を低めに設定することは、早期乾燥を促進するための手段の1つである。また、コーティング用薬剤の粘度を下げて流動性を高めておいて、物理的に厚く塗れないようにして、薄膜化を図る。早期乾燥を図る手段として、粘度を1000mPa・sec以下にすることが好ましい。刷毛塗り等の取り回しで薄くする工夫もできる。しかし、個人差が出るので、液粘度を低くして、流動性を高めて薄くする方法をとることが好ましい。また、粘度が低いために、タッチアップ的な部分補修部分への薬剤の入り込みが容易で、その部分を埋める補修にも有効になる。
コーティング用薬剤の条件は、上述の条件で規定された条件のものを採用する。
油井管のねじ継手のねじ山領域において軽度焼き付きが発生したときに、グラインダー、やすり、ペーパー等を使って焼き付き部分を養生する。養生後、その部分を薬剤で補修し、潤滑を再度確保する。このために、焼き付き箇所を含んでその周りだけか、若しくは、全面に塗布するようにして部分補修をすることができる。ねじ山領域において軽度焼き付き部分が補修された油井管ねじ継手は、再度、締付け締戻しが1回以上継続できるように改善することができる。
又は、別の油井管のねじ継手の潤滑向上を図るために、既にある固体潤滑被膜(一度も締付け締戻ししていない)の上に、本開示の薬剤を塗布してもうよい。この場合、本開示のコーティング用薬剤を塗らない場合に比べて、1回以上、締付け締戻しできるように、潤滑特性を改善することができる。
上述してきたコーティング用薬剤を使って形成された固体潤滑被膜の膜厚が10μm以上100μm以下であり、形成された固体潤滑被膜の膜硬度が、鉛筆硬度でB以下の軟質であることが好ましい。
この膜厚は、薬剤が乾いて固体潤滑被膜になった段階での膜厚である。その膜厚の特定は、例えば、ねじ部の円周方向に沿った4箇所(例えば、90度置きの4箇所)を長手方向に切断して得られる各断面について、それぞれ顕微鏡で観察することで実行する。その観察で、被膜の最も厚い部位と薄い部分とにおける各膜厚を特定する。そして、その各膜厚が、上記の範囲内か確認する。
なお、過去の測定結果から、膜厚分布の傾向が掴めている場合は、次のようにして膜厚を推定しても良い。すなわち、薬剤の塗布・乾燥方法が同じであれば、予め決めた特定の部位の膜厚を電磁膜厚計で測定することで、ねじ部全体における膜厚の最大値と最小値を推定することも可能である。
油井管ねじ構造のように、ねじ山がある構造であれば、なおさら、ねじ山の谷部分、特に、時計で言うところの6時位置では、コーティング用薬剤に溜る傾向も否定できない。また、薬液の表面張力によって、ねじ山構造の山のコーナー部分は薄くなる傾向もある。
形成した固体潤滑被膜の硬度は、H以下の鉛筆硬度であることが好ましい。
本開示の固体潤滑被膜は、あえて柔らかい膜質にして、強く当たったところでは、自らが僅かに削れていくことを想定して、潤滑特性の実現を図っているためである。膜の鉛筆硬度は、H以下の軟質であることが好ましい。Hを超えた高硬度のものでは、固体潤滑剤の黒鉛や金属石鹸を入れた際には、締付け締戻し時の衝撃で、脆く、根こそぎ取れてしまう場合がある。そして、それらが、ねじ間隙に詰まると、焼き付く懸念が高くなってしまう。軟質である方が好ましく、2B以下の鉛筆硬度がよく、更に好ましくは、4B以下の鉛筆硬度がよい。
本開示は、タッチアップ的な部分補修と、既にある固体潤滑被膜(一度も締付け締戻ししていない)の上に塗布して、潤滑特性を上げる目的で考案されたものである。
その特性を評価するにあたって、実井戸での締付けに沿った、油井管ねじの締付け締戻し条件にて、潤滑を評価することにする。ただし、実際の井戸や、模擬井戸で、油井管ねじの固体潤滑挙動を評価することは、コスト費用の点からも、実験手配の時間の観点からも現実的ではない。
以上のことから、固体潤滑被膜の潤滑評価では、実井戸模擬になるように工夫した新たな評価方法で評価する必要がある。
以上のような考えから、実施例での評価方法では、図6及び図7に示す装置を用いた重錘トング試験で評価した。模擬するのは、実際の井戸や模擬井戸で起こる締付け締戻試験を模擬する条件で、図3、図5で見られるような、締め込み条件になることを模擬して、固体潤滑被膜の潤滑性を評価するものである。
潤滑評価に対しては、上に述べてきた重錘トングを使った方法で、以下の判定基準を使って、可否判断した。
締付け締戻し回数に加えて、締戻し後、完全に緩んだら、ピンを上部に逃がして、ピンねじ表面と、ボックスねじ表面をエアーブロー後に観察して、焼き付きの有無を直接目視確認する。併せて、トルク・ターン・チャートを確認して、異常な点がないかを踏まえて判断するものとする。
本開示は、タッチアップ的な部分補修の効果を説明するために、人工的な焼き付きを以下のように作った。
まず、ボックスねじに、人工焼き付き用に特別な固体潤滑被膜を形成させた。具体的には、ボックスねじの全周に対して、1/8周分を紙でマスキングして、固体潤滑被膜用の薬剤をスプレー塗布した。その後、仮乾燥の後に焼成して、特殊な固体潤滑被膜を付けたボックスねじを作った。なお、マスキングしても、境界域は、膜厚が有り/無しの絶壁状の構造は作れず、マスキングの境界には不可避的な固体潤滑被膜の膜厚が徐々に薄くなりながらも形成された膜になった。一方で、マスキングした中心(紙マスキングの両端から見た中央付近)は、下地膜(リン酸Mn化成処理膜か、電気めっき膜)を露出させた状態になっている。その状態で締付け締戻しをすると、下地のリン酸Mn層や、電気メッキのみからなるマスキング分が焼き付き、焼き付くサンプルを再現よく作ることができる。なお、そのサンプルを評価する際にも、上で示した重錘トング試験方法を用いた。
(実施例1: 金属石鹸の調合の仕方)
本実施例1の検討群では、金属石鹸の混合方法について、液への混じり方で条件の選別を行った。
コーティング用薬剤の最終的な基本組成として、水系ポリマー、固体潤滑剤、水の重量比率を、40:20:40に調合した。ここに、重量比率相当で全薬剤重量100に対し1の割合でエタノールを混入させた。また、pH調整として僅かなアンモニア水を微添加した。
水系ポリマー(バインダー樹脂)として、酢酸ビニル100重量部に対しアクリル酸を10重量部として調合させてモノマーとして、酢酸ビニル、アクリル酸の共重合体を用いた。これは、結果として、アクリレートに属するポリマー100%の状態になった。
条件1は、金属石鹸および黒鉛を上記の調合比にしたがって、基礎薬剤中に直接投入して撹拌した事例である。工業用エタノールを一切使わない事例である。
条件1では、十分に混じり切らずに、表面に金属石鹸や黒鉛が浮いて互いに集合しているものがあったため、うまく均質に混ぜることができなかった。条件1は、これらの固体潤滑剤が撥水性を有し、水に不溶である従来からの知見を裏付けるような結果になった。
条件2は、金属石鹸と黒鉛を、上記の調合比にしたがって、基礎薬剤中に投入して撹拌して、Vol/Vol比で、水:100に対し工業用エタノール:2.5を、水からなる溶剤へ投入したものである。これは、上述のコーティング溶剤の最終的な基本組成「水系ポリマー、固体潤滑剤、水」を100重量部としたときに、1重量部に相当する。この事例は、金属石鹸や黒鉛が十分に混じり切らずに、表面に浮いて互いに集合しているものが見られたため、金属石鹸や黒鉛がうまく均質に混ぜることができなかった。条件2は、エタノールを後で混ぜても、金属石鹸や黒鉛はうまく混ざりきらないことを示している。
条件3は、水:100に対して、工業用エタノール:2.5の量とし、工業用エタノール中に金属石鹸と黒鉛を別容器で撹拌させてから、つまり均質に混じってから、基礎薬剤中に投入して撹拌した例である。条件3は、ほぼ均質に混じった例といえる。金属石鹸や黒鉛は、水に不溶と言われている。しかし、アルコール(工業用エタノール;エタノールが主成分)では、金属石鹸や黒鉛が、それぞれ、かつ、互いの粒が会合してダマになることなく、微細分散する状況が実現できるようであった。よって、一旦、金属石鹸を工業用エタノールに溶かしたあと、その状態を、基礎薬剤へ展開して撹拌することで、金属石鹸や黒鉛を均質に溶かした状況を作りだすことができることが分かった。
条件4は、水:100に対し工業用エタノール:0.5の量とし、工業用エタノール中に金属石鹸や黒鉛を別容器で十分撹拌させる。ただし、アルコール量が少なくて金属石鹸や黒鉛が溶解はしているものの、少量は混じっていない感じに見える状態で、基礎薬剤中に投入した。条件4は、そのあとに続けて、工業用エタノール:2の量を基礎薬剤中に投入して撹拌した例である。
工業用アルコールでの事前溶解したものを、水溶剤に投入すると、ほぼ均質に調整できた事例である。さらに、工業用エタノール:2だけ、更に、基礎薬剤へ投入することで、溶解が更に進んで、均質分散が実現できたように認識できた。
条件5は、水:100に対し工業用エタノール:2の量とし、工業用エタノール中に金属石鹸と黒鉛を別容器で十分撹拌させてから、基礎薬剤中に投入した。そのあとに続けて、工業用エタノール:0.5の量を基礎薬剤中に投入して撹拌した例である。この系では、金属石鹸であるステアリン酸Caと、黒鉛は、工業用エタノール:2に、既に均質に混じっている状態であった。したがって、その状態から、更に工業用エタノールを加えても、金属石鹸であるステアリン酸Caは、特に変化なく、均質に混じった例といえる。
(実施例2: 早期乾燥性と、塗布量と、固体潤滑剤の粒径、乾燥方法他の検討)
本実施例2の検討群は、油井管ねじの構造に塗って、乾燥具合で良悪を選別した事例である。
本実施例2では、アルコールとアンモニア水の調合比、アルコールの種別の違い、金属石鹸や黒鉛のサイズについて検討した。すなわち、下記の個々の薬剤の条件を変えたものを系統的に用意して、早期乾燥性について調査した。
水系ポリマー、固体潤滑剤、水の重量比率、その外数としての低級アルコール、アンモニア水の添加量は、水100に対する重量比で表現する。なお、アンモニア水(約28%-30%の濃アンモニア水)は、水系ポリマーの指摘するpH範囲になるように添加した。
共通の実験条件として、油井管ねじは、材料が炭素鋼、L80グレードで、サイズが、5.5” 23#、ねじがJFEBEARTMのピンねじで、短尺700-1000mm長さで両端に加工した油井管ねじとした。
乾燥を判断する位置は、油井管の上部側、時計で言うところの8時から4時位置の乾燥で判断した。なお、放置乾燥側でも同じ判断位置とした。
なお、この基礎薬剤の中に金属石鹸や黒鉛を混ぜる際には、実施例1の検討群で判明している方法「低級アルコール(エタノール:実施例1)」に金属石鹸を事前に混ぜてから混入方法を使った。ここで言う工業用エタノールとは、高純度なエタノールであるが、酒税法にかからないレベルで、メタノールやイソプロピルアルコールが混入しているものを指す。アルカリ石鹸については、薬剤の調合の最終段階で添加して撹拌させた。
その結果及び条件の詳細を、表1、2に示す。
No.2-2は、金属石鹸なし、黒鉛なし、溶剤に工業アルコール添加されている事例である。すなわち、金属石鹸や黒鉛が添加されていない事例である。潤滑特性のための、黒鉛や金属石鹸が入っていないので、比較例の扱いである。No.2-2は、アルコールの揮発を使っているので、乾燥時間が早くなっているが、送風乾燥の目標値5分を切れない例であり、比較例である。
No.2-3は、金属石鹸あり、黒鉛あり、アルコール無しの比較例である。金属石鹸や黒鉛は、表面積を増やすことで乾燥を促進させるためのものではある。しかし、アルコールを使わないので、金属石鹸が会合してしやすくダマになる。併せて黒鉛の溶解も若干ダマになる傾向があった。潤滑挙動を脇においたとしても、乾燥時間の基準条件(送風5分以下、静置乾燥30分以下)を同時に満たせないため、比較例にあたる。
No.2-6は、金属石鹸あり、黒鉛あり、アルコールありの本発明例である。本開示の規定範囲に、固体潤滑剤、アルコール、アンモニア等の組み合わせを設計することで、早期乾燥を実現できることを示している。
これに対して早期乾燥できたか、早期乾燥以外のパラメータ規定を満足しているかが判断基準となる。No.2-8~2-9は、金属石鹸である、ステアリン酸Caのサイズを変えた検討事例である。No.2-8~2-9は、共に早期乾燥の基準値を満たす本発明例である。No.2-8よりもNo.2-9の方が乾燥が速いのは、金属石鹸と黒鉛の粒径が1μmであり、No.2-8の5μmの粒径よりも細粒化して、表面積が増えたために、早期乾燥が促進されたためと推定される。
No.2-12~2-18の事例は、さまざまなアルコール種と、金属石鹸の検討を行ったものである。No.2-12~2-18の事例は、いずれも、早期乾燥の目標をクリアしており、本開示の規定の範囲であれば、早期乾燥性を満足することを示している。
実施例3の検討群では、実際の固体潤滑被膜で潤滑を持たせた油井管ねじを意図的に、人工的に焼き付きを起こした。そして、実施例3は、グラインダーや紙やすりで、焼き付き箇所を削り取るように養生した。その後、その部分を含めて、本開示で検討しているコーティング用薬剤の候補を塗って潤滑を検討した事例である。
その条件を表3、表4に示す。
締付け締戻し回数が1回以上増えたものについて、タッチアップ(≒リペア)できた発明例として扱う。次の締付け締戻し試験をした時に、再度焼き付いたものは、比較例に位置付けるよう判断した。手直し後に3回以上の締付け締戻し回数ができたものは一層優れると判断できる。表5、表6が本実施例の条件や結果である。
焼き付き後に、その場所をグラインダーや、やすりや、研磨紙で養生したあと、コーティング用薬剤を塗布した。バインダー樹脂を、酢酸ビニル-ブチルアクリレート、ポリビニールの共重合体として、金属石鹸、黒鉛、アルコール、アンモニア等を調合したものを塗布して、再度、締付け締戻しを再開した。
No.3-3は、黒鉛のサイズが好適な規定を超えて大きい例である、1回分は、さらに締付け締戻しができるよう改善できている。しかし、改善効果は大きくはない。No.3-4は、固体潤滑剤が多すぎた、つまり、黒鉛が多めに配合された比較例である。
No.3-5は、逆に、固体潤滑剤が少なすぎた事例である。これらは共に、タッチアップ的な部分補修後に、締付け締戻しを改善することなく、ただちに焼き付いた比較例である。No.3-4は、固体潤滑剤が多すぎ、つまり、黒鉛が多すぎて、黒テープ状の2次生成物が、ねじ間隙に詰まってしまって焼き付いた。No.3-5は、逆に、固体潤滑被膜の潤滑剤成分が少ないため、潤滑不足に陥って焼き付いたと考えられる。
一方で、No.3-8は、固体潤滑剤の割合が多い事例である。No.3-9は、水系ポリマーの割合が多い事例である。No.3-10は、水が多い事例である。No.3-8~3-10は、固体潤滑被膜の安定度がよくなくて、必要な潤滑を確保できずに、補修後にも、焼き付いてしまった比較例である。
一方で、No.3-13は、黒鉛が多すぎた事例である。水系組成のペイントに事前にアルコールに混ぜてから投入してもダマになる傾向があって、その影響も懸念される比較例である。No.3-14は、金属石鹸を入れない事例であり、比較例にあたる。No.3-14は、補修後には潤滑は復活しなかった。つまり、黒鉛だけの潤滑剤だけは達成しえない潤滑があり、これらの協働で潤滑が達成していることを示唆する結果になった。No.3-15は、逆に、黒鉛がない系で、金属石鹸だけの系の事例であるが、比較例にあたる。No.3-15から、水系の溶剤には、アルコールでの事前溶解をもってしても、金属石鹸は混ざりきらず、ダマになることを含めて、潤滑が足りなかったと推定される。
実施例4のNo.4-1~4-5の事例は、前の実施例3で使った固体潤滑被膜に対して、2つの並行的な比較試験を行ったものである。1つは、単に、締付け締戻し試験を行って、その締付け締戻し回数を調査することである。その上で、締付け前に、本開示の薬剤を表面に一様に塗って、締付け締戻し回数を調査するべく、重錘トング試験を行い、その回数の変化で改善の有無を知る方法である。今回は、焼き付きを意図的に作らず、一様な膜を形成させた。
その結果を表7~表10に示す。
No.4-1-B、4-1-P、4-1-BPの事例は、順に、ボックスねじ(雌ネジ)のみ、ピンねじ(雄ネジ)のみ、ボックスねじ・ピンねじ両方に、本開示の薬剤を潤滑補助剤として適用した事例である。No.4-1-BP2の事例は、ピンねじ表面に3-P2の薬剤で形成させた固体樹脂被膜ではなくて、実施例3のNo.3-1の条件の薬剤を使って、固体潤滑被膜を形成させた事例である。
No.4-1-BP2は、ピンねじ側の固体潤滑膜:3-P2を、本開示の潤滑補助膜に置換した条件である。この場合には、潤滑補助膜は、ピンねじ側の固体潤滑被膜自体としても機能することがわかり、潤滑特性を実現できることがわかる。
No.4-4-B-0、4-4-B-0.5、4-4-B-1.0、4-4-B-3.0、4-4-B-5.0、4-4-B-8.0の事例は、規定範囲内にあるコーティング用薬剤をボックスねじ側に潤滑補助効果を期待した事例である。これらの事例は、黒鉛の含有量を、全固体潤滑剤重量に対して黒鉛の添加量を、順に、0.0%、0.5%、1.0%、3.0%、5.0%、8.0%の条件で比較検討調査した結果である。
No.4-5-Bの例は、既に、潤滑サポートを行わなくても、既に、評価結果が、3回のトライとも、≧10回の締付け締戻し回数が実現できているので、その改善が評価出来なかった。しかし、一層の厳しい潤滑条件では、少なからず改善の効果があることが、No.4-1~4-4の事例から推察できる。
本開示は、次の構成も取り得る。
(1)金属面に塗布して固体潤滑被膜を形成するためのコーティング用薬剤であって、
固体潤滑剤と、バインダー樹脂と、溶剤とを主成分とし、
上記溶剤は、水を主成分とし、その水に対し炭素数3以下の低級アルコールが添加物として添加され、上記添加物の体積は、水の体積100に対し0.5以上10以下であり、
上記溶剤の体積の95%以上が、上記水と上記添加物で構成され、
上記固体潤滑剤として、黒鉛と金属石鹸を全固体潤滑成分重量の95%以上含み、
更に上記固体潤滑剤として、アルカリ石鹸を全固体潤滑成分重量の0%以上1%以下含み、
上記黒鉛は、重量比で、全固体潤滑剤の0.5%以上5%以下であり、
上記バインダー樹脂は、水溶性若しくは水分散性のポリマーであって、そのポリマーは、アクリレート又はメタクリレートに属するモノマーを上記バインダー樹脂全重量の90%以上含む、ポリマー又は共重合体である。
(2)上記添加物として、更にアンモニア水が添加されている。
(3)上記バインダー樹脂が、薬剤全重量の30%以上40%以下であり、
上記固体潤滑剤が、薬剤全重量の10%以上20%以下であり、
上記溶剤が、薬剤全重量の40%以上50%以下である。
(4)溶剤成分として、上記溶剤を構成する水に、低級アルコール及びアンモニア水のうち、少なくとも低級アルコールが添加物として添加され、上記低級アルコールは、1種類又は2種類以上の、炭素数3以下の低級アルコールからなり、
上記低級アルコールの体積は、溶剤を構成する水の体積100に対し0.5以上10以下であり、
上記アンモニア水の体積は、溶剤を構成する水の体積100に対し0以上5以下である。
(5)上記低級アルコールは、メタノール、エタノール、イソプロピルアルコール、ノルマルプロピルアルコール、工業用エタノールから選択した低級アルコールである。
(6)上記黒鉛の平均粒径が、5μm以下であり、
上記金属石鹸の平均粒径が、5μm以下である。
(7)上記バインダー樹脂を構成する水溶性若しくは水分散性のポリマーは、下記(1)~(4)に記載のモノマーのうち、単体で構成されるポリマー、又は、下記(1)~(4)に記載のモノマーの2個以上のモノマーならなる共重合体である。
(1)アクリレート、メタクリレート、及び、これらの個々の誘導体を主体とするモノマー
(2)アクリレート、メタクリレート、これらの個々の誘導体に、アルキルエステル、ビニルエステル、スチレンエステル、カルボン酸エステル、及び、これらの個々の誘導体を含んだモノマーと一体となったモノマー
(3)上記(1)(2)に対してグラフト化したモノマー
(4)ビニル化合物、ウレタン化合物のうちのいずれか一方か両方のモノマーが、少なくとも(1)~(3)のうちの1つ以上のモノマーと一体となって構成されるモノマー
(8)上記金属石鹸として、下記のA群から選択した脂肪酸と下記のB群から選択した金属元素からなる化合物である金属石鹸を1種類若しくは2種類以上含み、
上記アルカリ石鹸として、下記のA群から選択した脂肪酸と下記のC群から選択した金属元素からなる化合物であるアルカリ石鹸を1種類若しくは2種類以上含む。
A群:ステアリン酸、ベヘン酸、ラウリン酸、12-ヒドロキシステアリン酸、オレイン酸、モンタン酸
B群:Mg、Ca、Zn、Ba
C群:Na、K
(9)薬剤の引火点が60℃以上、又は不燃性の、本開示のコーティング用薬剤。
(10)薬剤の粘度が、1000mPa・sec以下である、本開示のコーティング用薬剤。
(11)金属面に対し塗布量0.1g/mm2以下で塗布し、常温大気環境で放置乾燥をした場合、30分以内に乾燥可能な早期乾燥性を有する。
(12)金属面に対し塗布量0.1g/mm2以下で塗布し、常温大気環境で1m/秒以上の送風乾燥をした場合、3分以内に乾燥可能な早期乾燥性を有する。
(13)本開示のコーティング用薬剤の製造方法であって、
上記低級アルコールに上記金属石鹸を分散混濁させたあと、溶剤の水へ投入することによって、上記金属石鹸の調合を行う。
(14)油井管のねじ部の潤滑膜を補修する油井管補修方法であって、
油井管のねじ部のうち、焼き付きが発生した領域を養生したのちに、少なくとも上記養生部分に対し、本開示のコーティング用薬剤を塗布する。
(15)固体潤滑被膜がねじ部に形成された油井管に対し、上記固体潤滑被膜の上に、本開示のコーティング用薬剤を塗布する。
(16)固体潤滑被膜を有する潤滑被膜がねじ部に形成された油井管であって、
上記固体潤滑被膜は、バインダー樹脂に固体潤滑剤が分散して構成され、
上記固体潤滑剤として、黒鉛と金属石鹸を全固体潤滑成分重量の95%以上であり、
更に上記固体潤滑剤として、アルカリ石鹸を全固体潤滑成分重量の0%以上1%以下含み、
上記黒鉛は、重量比で、全固体潤滑剤の0.5%以上5%以下であり、
上記バインダー樹脂は、水溶性若しくは水分散性のポリマーであって、そのポリマーは、アクリレート又はメタクリレートに属するモノマーを上記バインダー樹脂全重量の90%以上含む、ポリマー又は共重合体である。
(17)上記黒鉛の平均粒径が、5μm以下であり、
上記金属石鹸の平均粒径が、5μm以下である。
(18)上記金属石鹸は、重量比で、全固体潤滑剤の0.5%以上5%以下である。
(19)上記バインダー樹脂を構成する水溶性若しくは水分散性のポリマーは、下記(1)~(4)に記載のモノマーのうち、単体で構成されるポリマー、又は、下記(1)~(4)に記載のモノマーの2個以上のモノマーならなる共重合体である。
(1)アクリレート、メタクリレート、及び、これらの個々の誘導体を主体とするモノマー
(2)アクリレート、メタクリレート、これらの個々の誘導体に、アルキルエステル、ビニルエステル、スチレンエステル、カルボン酸エステル、及び、これらの個々の誘導体を含んだモノマーと一体となったモノマー
(3)上記(1)(2)に対してグラフト化したモノマー
(4)ビニル化合物、ウレタン化合物のうちのいずれか一方か両方のモノマーが、少なくとも(1)~(3)のうちの1つ以上のモノマーと一体となって構成されるモノマー
(20)上記金属石鹸として、下記のA群から選択した脂肪酸と下記のB群から選択した金属元素からなる化合物である金属石鹸を1種類若しくは2種類以上含み、
上記アルカリ石鹸として、下記のA群から選択した脂肪酸と下記のC群から選択した金属元素からなる化合物であるアルカリ石鹸を1種類若しくは2種類以上含む。
A群:ステアリン酸、ベヘン酸、ラウリン酸、12-ヒドロキシステアリン酸、オレイン酸、モンタン酸
B群:Mg、Ca、Zn、Ba
C群:Na、K
(21)上記固体潤滑被膜は、膜厚が10μm以上100μm以下であり、膜硬度が、鉛筆硬度でB以下の軟質である。
1a ねじ部
2 ボックス
2a ねじ部
Claims (21)
- 金属面に塗布して固体潤滑被膜を形成するためのコーティング用薬剤であって、
固体潤滑剤と、バインダー樹脂と、溶剤とを主成分とし、
上記溶剤は、水を主成分とし、その水に対し炭素数3以下の低級アルコールが添加物として添加され、上記添加物の体積は、水の体積100に対し0.5以上10以下であり、
上記溶剤の体積の95%以上が、上記水と上記添加物で構成され、
上記固体潤滑剤として、黒鉛と金属石鹸を全固体潤滑成分重量の95%以上含み、
更に上記固体潤滑剤として、アルカリ石鹸を全固体潤滑成分重量の0%以上1%以下含み、
上記黒鉛は、重量比で、全固体潤滑剤の0.5%以上5%以下であり、
上記バインダー樹脂は、水溶性若しくは水分散性のポリマーであって、そのポリマーは、アクリレート又はメタクリレートに属するモノマーを上記バインダー樹脂の全重量の90%以上含む、ポリマー又は共重合体である、
固体潤滑被膜を形成するためのコーティング用薬剤。 - 上記添加物として、更にアンモニア水が添加されている、
請求項1に記載した固体潤滑被膜を形成するためのコーティング用薬剤。 - 上記バインダー樹脂が、薬剤全重量の30%以上40%以下であり、
上記固体潤滑剤が、薬剤全重量の10%以上20%以下であり、
上記溶剤が、薬剤全重量の40%以上50%以下である、
請求項1又は請求項2に記載した固体潤滑被膜を形成するためのコーティング用薬剤。 - 溶剤成分として、上記溶剤を構成する水に、低級アルコール及びアンモニア水のうち、少なくとも低級アルコールが添加物として添加され、上記低級アルコールは、1種類又は2種類以上の、炭素数3以下の低級アルコールからなり、
上記低級アルコールの体積は、溶剤を構成する水の体積100に対し0.5以上10以下であり、
上記アンモニア水の体積は、溶剤を構成する水の体積100に対し0以上5以下である、
請求項1~請求項3のいずれか1項に記載した固体潤滑被膜を形成するためのコーティング用薬剤。 - 上記低級アルコールは、メタノール、エタノール、イソプロピルアルコール、ノルマルプロピルアルコール、工業用エタノールから選択した低級アルコールである、
請求項1~請求項4のいずれか1項に記載した固体潤滑被膜を形成するためのコーティング用薬剤。 - 上記黒鉛の平均粒径が、5μm以下であり、
上記金属石鹸の平均粒径が、5μm以下である、
請求項1~請求項5のいずれか1項に記載した固体潤滑被膜を形成するためのコーティング用薬剤。 - 上記バインダー樹脂を構成する水溶性若しくは水分散性のポリマーは、下記(1)~(4)に記載のモノマーのうち、単体で構成されるポリマー、又は、下記(1)~(4)に記載のモノマーの2個以上のモノマーならなる共重合体である、
請求項1~請求項6のいずれか1項に記載した固体潤滑被膜を形成するためのコーティング用薬剤。
(1)アクリレート、メタクリレート、及び、これらの個々の誘導体を主体とするモノマー
(2)アクリレート、メタクリレート、これらの個々の誘導体に、アルキルエステル、ビニルエステル、スチレンエステル、カルボン酸エステル、及び、これらの個々の誘導体を含んだモノマーと一体となったモノマー
(3)上記(1)(2)に対してグラフト化したモノマー
(4)ビニル化合物、ウレタン化合物のうちのいずれか一方か両方のモノマーが、少なくとも(1)~(3)のうちの1つ以上のモノマーと一体となって構成されるモノマー - 上記金属石鹸として、下記のA群から選択した脂肪酸と下記のB群から選択した金属元素からなる化合物である金属石鹸を1種類若しくは2種類以上含み、
上記アルカリ石鹸として、下記のA群から選択した脂肪酸と下記のC群から選択した金属元素からなる化合物であるアルカリ石鹸を1種類若しくは2種類以上含む、
請求項1~請求項7のいずれか1項に記載した固体潤滑被膜を形成するためのコーティング用薬剤。
A群:ステアリン酸、ベヘン酸、ラウリン酸、12-ヒドロキシステアリン酸、オレイン酸、モンタン酸
B群:Mg、Ca、Zn、Ba
C群:Na、K - 薬剤の引火点が60℃以上、又は不燃性の、請求項1~請求項8のいずれか1項に記載した固体潤滑被膜を形成するためのコーティング用薬剤。
- 薬剤の粘度が、1000mPa・sec以下である、請求項1~請求項9のいずれか1項に記載した固体潤滑被膜を形成するためのコーティング用薬剤。
- 金属面に対し塗布量0.1g/mm2以下で塗布し、常温大気環境で放置乾燥をした場合、30分以内に乾燥可能な早期乾燥性を有する、請求項1~請求項10のいずれか1項に記載した固体潤滑被膜を形成するためのコーティング用薬剤。
- 金属面に対し塗布量0.1g/mm2以下で塗布し、常温大気環境で1m/秒以上の送
風乾燥をした場合、3分以内に乾燥可能な早期乾燥性を有する、請求項1~請求項11のいずれか1項に記載した固体潤滑被膜を形成するためのコーティング用薬剤。 - 請求項1~請求項12のいずれか1項に記載したコーティング用薬剤の製造方法であって、
上記低級アルコールに上記金属石鹸を分散混濁させたあと、溶剤の水へ投入することによって、上記金属石鹸の調合を行う、
固体潤滑被膜を形成するためのコーティング用薬剤の製造方法。 - 油井管のねじ部の潤滑膜を補修する油井管補修方法であって、
油井管のねじ部のうち、焼き付きが発生した領域を養生したのちに、少なくとも上記養生部分に対し、請求項1~請求項12のいずれか1項に記載した固体潤滑被膜を形成するためのコーティング用薬剤を塗布する、
油井管補修方法。 - 固体潤滑被膜がねじ部に形成された油井管に対し、上記固体潤滑被膜の上に、請求項1~請求項12のいずれか1項に記載した固体潤滑被膜を形成するためのコーティング用薬剤を塗布する、
油井管の潤滑改善方法。 - 固体潤滑被膜を有する潤滑被膜がねじ部に形成された油井管であって、
上記固体潤滑被膜は、バインダー樹脂に固体潤滑剤が分散して構成され、
上記固体潤滑剤として、黒鉛と金属石鹸を全固体潤滑成分重量の95%以上であり、
更に上記固体潤滑剤として、アルカリ石鹸を全固体潤滑成分重量の0%以上1%以下含み、
上記黒鉛は、重量比で、全固体潤滑剤の0.5%以上5%以下であり、
上記バインダー樹脂は、水溶性若しくは水分散性のポリマーであって、そのポリマーは、アクリレート又はメタクリレートに属するモノマーを上記バインダー樹脂の全重量の90%以上含む、ポリマー又は共重合体である、
油井管。 - 上記黒鉛の平均粒径が、5μm以下であり、
上記金属石鹸の平均粒径が、5μm以下である、
請求項16に記載した油井管。 - 上記金属石鹸は、重量比で、全固体潤滑剤の0.5%以上5%以下である、
請求項16又は請求項17に記載した油井管。 - 上記バインダー樹脂を構成する水溶性若しくは水分散性のポリマーは、下記(1)~(4)に記載のモノマーのうち、単体で構成されるポリマー、又は、下記(1)~(4)に記載のモノマーの2個以上のモノマーならなる共重合体である、
請求項16~請求項18のいずれか1項に記載した油井管。
(1)アクリレート、メタクリレート、及び、これらの個々の誘導体を主体とするモノマー、
(2)アクリレート、メタクリレート、これらの個々の誘導体に、アルキルエステル、ビニルエステル、スチレンエステル、カルボン酸エステル、及び、これらの個々の誘導体を含んだモノマーと一体となったモノマー、
(3)上記(1)(2)に対してグラフト化したモノマー、
(4)ビニル化合物、ウレタン化合物のうちのいずれか一方か両方のモノマーが、少なくとも(1)~(3)のうちの1つ以上のモノマーと一体となって構成されるモノマー - 上記金属石鹸として、下記のA群から選択した脂肪酸と下記のB群から選択した金属元素からなる化合物である金属石鹸を1種類若しくは2種類以上含み、
上記アルカリ石鹸として、下記のA群から選択した脂肪酸と下記のC群から選択した金属元素からなる化合物であるアルカリ石鹸を1種類若しくは2種類以上含む、
請求項16~請求項19のいずれか1項に記載した油井管。
A群:ステアリン酸、ベヘン酸、ラウリン酸、12-ヒドロキシステアリン酸、オレイン酸、モンタン酸
B群:Mg、Ca、Zn、Ba
C群:Na、K - 上記固体潤滑被膜は、膜厚が10μm以上100μm以下であり、膜硬度が、鉛筆硬度でB以下の軟質である、
請求項16~請求項19のいずれか1項に記載した油井管。
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202380060476.1A CN119654382A (zh) | 2022-08-25 | 2023-08-14 | 用于形成固体润滑被膜的涂布用试剂、该涂布用试剂的制造方法、油井管修补方法、油井管的润滑改善方法和油井管 |
| JP2023570233A JP7498471B1 (ja) | 2022-08-25 | 2023-08-14 | 固体潤滑被膜を形成するためのコーティング用薬剤、そのコーティング用薬剤の製造方法、油井管補修方法、油井管の潤滑改善方法、及び油井管 |
| EP23857245.7A EP4559986A4 (en) | 2022-08-25 | 2023-08-14 | CHEMICAL COATING AGENT FOR FORMING SOLID LUBRICATING FILM AND METHOD FOR PRODUCING SAME, METHOD FOR REPAIRING OIL WELL PIPE, METHOD FOR IMPROVING LUBRICATION OF OIL WELL PIPE, AND OIL WELL PIPE |
| MX2025002223A MX2025002223A (es) | 2022-08-25 | 2025-02-24 | Agente de recubrimiento para formar una pelicula de recubrimiento lubricante solido, metodo para fabricar el agente de recubrimiento, metodo para reparar tuberia de uso petrolero, metodo para mejorar la lubricacion de tuberia de uso petrolero, y tuberia de uso petrolero |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022134376 | 2022-08-25 | ||
| JP2022-134376 | 2022-08-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024043132A1 true WO2024043132A1 (ja) | 2024-02-29 |
Family
ID=90013191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2023/029434 Ceased WO2024043132A1 (ja) | 2022-08-25 | 2023-08-14 | 固体潤滑被膜を形成するためのコーティング用薬剤、そのコーティング用薬剤の製造方法、油井管補修方法、油井管の潤滑改善方法、及び油井管 |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP4559986A4 (ja) |
| JP (1) | JP7498471B1 (ja) |
| CN (1) | CN119654382A (ja) |
| AR (1) | AR130263A1 (ja) |
| MX (1) | MX2025002223A (ja) |
| WO (1) | WO2024043132A1 (ja) |
Citations (6)
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|---|---|---|---|---|
| JPS6284193A (ja) * | 1985-09-11 | 1987-04-17 | Kobe Steel Ltd | 金属の引抜き加工用潤滑剤 |
| JPH1036876A (ja) * | 1996-07-24 | 1998-02-10 | Makoto Futsukusu Kk | 潤滑剤組成物 |
| JP2008537062A (ja) * | 2005-03-29 | 2008-09-11 | 住友金属工業株式会社 | 鋼管用ねじ継手 |
| WO2009072486A1 (ja) * | 2007-12-04 | 2009-06-11 | Sumitomo Metal Industries, Ltd. | 管ねじ継手 |
| JP2014501885A (ja) * | 2010-11-05 | 2014-01-23 | 新日鐵住金株式会社 | 高トルク締付け特性に優れた管ねじ継手 |
| JP2022134376A (ja) | 2021-03-03 | 2022-09-15 | ローム株式会社 | Memsセンサ及びその製造方法、並びにmemsパッケージ。 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH08300087A (ja) * | 1995-05-09 | 1996-11-19 | Sumitomo Metal Ind Ltd | 耐型かじり性・脱膜性に優れた潤滑処理方法 |
| AU2003241890A1 (en) * | 2002-05-31 | 2003-12-19 | Sumitomo Metal Industries, Ltd. | Screw joint for steel pipe |
-
2023
- 2023-08-14 WO PCT/JP2023/029434 patent/WO2024043132A1/ja not_active Ceased
- 2023-08-14 JP JP2023570233A patent/JP7498471B1/ja active Active
- 2023-08-14 EP EP23857245.7A patent/EP4559986A4/en active Pending
- 2023-08-14 CN CN202380060476.1A patent/CN119654382A/zh active Pending
- 2023-08-22 AR ARP230102216A patent/AR130263A1/es unknown
-
2025
- 2025-02-24 MX MX2025002223A patent/MX2025002223A/es unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6284193A (ja) * | 1985-09-11 | 1987-04-17 | Kobe Steel Ltd | 金属の引抜き加工用潤滑剤 |
| JPH1036876A (ja) * | 1996-07-24 | 1998-02-10 | Makoto Futsukusu Kk | 潤滑剤組成物 |
| JP2008537062A (ja) * | 2005-03-29 | 2008-09-11 | 住友金属工業株式会社 | 鋼管用ねじ継手 |
| WO2009072486A1 (ja) * | 2007-12-04 | 2009-06-11 | Sumitomo Metal Industries, Ltd. | 管ねじ継手 |
| JP2014501885A (ja) * | 2010-11-05 | 2014-01-23 | 新日鐵住金株式会社 | 高トルク締付け特性に優れた管ねじ継手 |
| JP2022134376A (ja) | 2021-03-03 | 2022-09-15 | ローム株式会社 | Memsセンサ及びその製造方法、並びにmemsパッケージ。 |
Non-Patent Citations (3)
| Title |
|---|
| See also references of EP4559986A4 |
| STEVEN S. SHADEMANJOHN W. MARTINAL P. DAVIS, NACE CORROSION, no. 2012-1095, 2012 |
| TSURU ET AL., JOURNAL OF THE JAPANESE ASSOCIATION FOR PETROLEUM TECHNOLOGY, vol. 61, no. 6, 1996, pages 527 - 536 |
Also Published As
| Publication number | Publication date |
|---|---|
| MX2025002223A (es) | 2025-04-02 |
| EP4559986A4 (en) | 2025-10-22 |
| EP4559986A1 (en) | 2025-05-28 |
| CN119654382A (zh) | 2025-03-18 |
| JP7498471B1 (ja) | 2024-06-12 |
| JPWO2024043132A1 (ja) | 2024-02-29 |
| AR130263A1 (es) | 2024-11-20 |
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