WO2015133545A1 - ダウンホールツール用分解性ゴム部材、分解性シール部材、分解性保護部材、ダウンホールツール、及び坑井掘削方法 - Google Patents
ダウンホールツール用分解性ゴム部材、分解性シール部材、分解性保護部材、ダウンホールツール、及び坑井掘削方法 Download PDFInfo
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- WO2015133545A1 WO2015133545A1 PCT/JP2015/056419 JP2015056419W WO2015133545A1 WO 2015133545 A1 WO2015133545 A1 WO 2015133545A1 JP 2015056419 W JP2015056419 W JP 2015056419W WO 2015133545 A1 WO2015133545 A1 WO 2015133545A1
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- rubber
- downhole tool
- degradable
- decomposable
- downhole
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Classifications
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B29/00—Cutting or destroying pipes, packers, plugs or wire lines, located in boreholes or wells, e.g. cutting of damaged pipes, of windows; Deforming of pipes in boreholes or wells; Reconditioning of well casings while in the ground
- E21B29/02—Cutting or destroying pipes, packers, plugs or wire lines, located in boreholes or wells, e.g. cutting of damaged pipes, of windows; Deforming of pipes in boreholes or wells; Reconditioning of well casings while in the ground by explosives or by thermal or chemical means
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/012—Additives activating the degradation of the macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0033—Additives activating the degradation of the macromolecular compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
- C08K5/1575—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/426—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/12—Packers; Plugs
- E21B33/1208—Packers; Plugs characterised by the construction of the sealing or packing means
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B2200/00—Special features related to earth drilling for obtaining oil, gas or water
- E21B2200/08—Down-hole devices using materials which decompose under well-bore conditions
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
- E21B33/134—Bridging plugs
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
Definitions
- the present invention relates to a degradable rubber member for a downhole tool, such as a well drilling plug, a degradable seal member, and a degradable protective member used in well drilling to produce hydrocarbon resources such as oil or natural gas. , Downhole tool, and well drilling method.
- Hydrocarbon resources such as oil or natural gas have been mined and produced through wells (oil wells or gas wells, sometimes called “wells”) that have porous and permeable underground layers. With the increase in energy consumption, the wells have been deepened, and there are records of excavation exceeding 9000m in the world, and there are also deep wells exceeding 6000m in Japan.
- the acid treatment and the crushing method are known as the stimulation method.
- Acid treatment increases the permeability of the production layer by injecting a mixture of strong acids such as hydrochloric acid and hydrogen fluoride into the production layer and dissolving the rock reaction components (carbonates, clay minerals, silicates, etc.)
- strong acids such as hydrochloric acid and hydrogen fluoride
- rock reaction components carbonates, clay minerals, silicates, etc.
- various problems associated with the use of strong acids have been pointed out, and an increase in cost has been pointed out including various countermeasures.
- fracturing method also referred to as “fracturing method” or “hydraulic fracturing method”
- the hydraulic fracturing method is a method in which a production layer is cracked by a fluid pressure such as water pressure (hereinafter sometimes simply referred to as “water pressure”).
- a fluid pressure such as water pressure (hereinafter sometimes simply referred to as “water pressure”).
- water pressure a fluid pressure
- a vertical hole is excavated, followed by a vertical hole.
- these well holes which means holes to form wells, sometimes referred to as “down holes”.
- Fracturing fluid is fed into the tank at a high pressure, and cracks (fractures) are generated by water pressure in deep underground production layers (layers that produce hydrocarbon resources such as oil or natural gas), and hydrocarbon resources are collected through the fractures.
- It is a production layer stimulation method for.
- the hydraulic fracturing method has attracted attention for its effectiveness in the development of unconventional resources such as so-called shale oil (oil aged in shale) and shale gas.
- a high-pressure fluid such as a fracturing fluid
- water pressure causes cracks (fractures) in deep underground production layers (layers that produce hydrocarbon resources such as oil such as shale oil or natural gas such as shale gas)
- fractures deep underground production layers
- layers layers that produce hydrocarbon resources such as oil such as shale oil or natural gas such as shale gas
- the following methods are usually employed. That is, for a well hole (downhole) excavated in the formation of several thousand meters underground, the predetermined section is partially blocked while sequentially closing from the tip of the well hole, and the blockage is blocked.
- the production layer is cracked or perforated using a tool containing a high-pressure fluid such as a fracturing fluid in the compartment or a gun containing a gunpowder such as a perforation gun.
- the next predetermined section (usually, a section before the preceding section, that is, a section on the ground side) is closed and fracturing or the like is performed, and cracks and perforations are advanced. Thereafter, this process is repeated until the necessary sealing and fracturing are completed.
- the production layer may be stimulated again by fracturing the desired section of the well hole that has already been formed. In that case as well, operations for blocking and fracturing the well hole may be repeated. Further, in order to finish the well, the well hole may be closed to shut off the fluid from the lower part, and after the upper part is finished, the closing may be released.
- a plug (“flac plug”, “bridge plug”, or “packer”) that closes and fixes a well hole by arranging various members (elements) around a cored bar. Etc.) are also disclosed.
- Patent Document 1 discloses an expandable and decomposable plug in which a metal slip, an elastomer seal, or the like is disposed on the outer peripheral surface of a mandrel.
- a slip, a conical member, a malleable element formed from an elastomer or rubber, or the like is arranged on a peripheral surface of a mandrel, and a ball or a flapper (
- a degradable downhole plug with an impediment such as a flapper is disclosed.
- slip, a packer element assembly (packer element assembly) composed of a plurality of sealing elements, etc. are arranged on the outer peripheral surface of a long cylindrical body member (tubular body element).
- a biodegradable downhole tool flac plug
- a fracture sleeve piston (fractureractsleeve piston, sometimes referred to as “piston” or “piston plug”) provided through a passageway in the center is moved in the axial direction of the sleeve.
- a ball sealer (sometimes referred to as “ball”) and a ball valve seat (also referred to as “ball seat” or simply “seat”)
- a sleeve system (sometimes referred to as “flux leave”) that sequentially forms a closed space is disclosed.
- Downhole tools used for well drilling are sequentially placed in the wellbore until the well is completed, and the borehole tool is used to perform well treatment such as fracturing and drilling with high-pressure fluid.
- a sealing performance is required that can block (seal) a required section of the inside against a fluid pressure.
- any well treatment is finished and the next well treatment is to be performed, it is required that the seal can be easily released.
- oil or natural gas such as shale gas
- Downhole tools such as plugs are usually not designed to be released and recovered after use, so they can be broken or shredded by milling, drilling out, or other methods. However, it has been necessary to spend a lot of money and time for crushing and drilling.
- plugs that can be recovered after use (retrievable plug), but since the plugs are deep underground, recovering all of them requires a lot of money and time. Was.
- downhole tools used for well drilling are sequentially placed in the well until the well is completed, subjected to well treatment such as fracturing and drilling with high-pressure fluid,
- Various sensors, flow paths, etc. are arranged as downhole tool members so that the well treatment is completed, the seal is released, and the next well treatment can be sequentially performed repeatedly.
- These sensors and flow paths are damaged by friction, contact and collision with other members when downhole tools are placed in underground wells, and by high pressure fluids used in well treatment.
- a rubber material such as urethane rubber is used.
- a downhole tool protection member that protects the sensor, the flow path, and the like has been required to have a function that can be easily removed or collected together with a protection function for the sensor, the flow path, and the like.
- Patent Document 1 discloses that slips and mandrels are formed from degradable metal elements such as reactive metals.
- Patent Document 2 discloses that a flapper, a ball, or the like that decomposes at a predetermined temperature, pressure, pH, or the like is provided.
- Patent Document 3 discloses that a plug or a member thereof is formed from a biodegradable material (formed from biodegradable materials), but does not disclose specific use.
- Patent Document 4 does not disclose that the flux leave is degradable.
- mining conditions such as deepening have become increasingly severe
- Diversification of mining conditions for example, mining under various environmental conditions such as a temperature condition of less than 60 ° C. to about 200 ° C. is accompanied with the diversification of depth. That is, downhole tool members used for downhole tools such as flack plugs, bridge plugs, packers, cement retainers, and sleeve systems (flux leaves) can be transported to a depth of several thousand meters.
- the environmental conditions of the well such as the temperature conditions associated with the diversification of depth, etc.
- the environmental conditions of the well such as the temperature conditions associated with the diversification of depth, etc.
- it is required to have the characteristics that it can be easily removed within a desired period and that the fluid seal can be completely released to improve the production efficiency. It has become like this.
- the downhole tool protection member has been required to have a characteristic that protects the sensor, the flow path, and the like while the downhole tool is disposed and the well treatment is performed, and can be easily removed thereafter.
- the first aspect of the subject of the present invention is that the mining conditions such as the deepening are various, and the mine requires a sealing operation including drilling and fracturing by securely sealing the fluid.
- the seal function is reliably maintained for a desired period of time in various downhole environments, and the seal is released for removal and flow in a desired period of time.
- the ability to design as desired so that the road can be secured contributes to cost reduction and process shortening, and contributes to the improvement of production efficiency. By protecting the sensor and the flow path during the well treatment, and having the characteristics that can be easily removed afterwards, it contributes to cost reduction and process shortening as well as improving production efficiency.
- the other side of the subject of this invention is providing the downhaul tool provided with this rubber member.
- Still another aspect of the present invention is to provide a well excavation method using the rubber member.
- the decomposable rubber member for downhole tools is formed from a rubber material containing a predetermined amount of a decomposition accelerator in the decomposable rubber.
- the present invention has been completed.
- the down is characterized by being formed from a rubber material containing 0.1 to 20 parts by mass of a decomposition accelerator with respect to 100 parts by mass of the degradable rubber.
- a degradable rubber member for hall tools is provided.
- the following decomposable rubber member for downhole tools (2) to (4) is provided.
- (2) It is formed from a rubber material containing 0.1 to 20 parts by mass of a decomposition accelerator with respect to 100 parts by mass of degradable rubber, and has a mass after being immersed in water at a temperature of 150 ° C. for 24 hours or 50% strain compression stress.
- the following decomposable rubber member for downhole tools (5) to (23) is provided.
- (5) Decomposition for a downhole tool according to any one of (1) to (4) above, wherein the tensile breaking strain at a temperature of 66 ° C. is 50% or more, the 70% strain compressive stress is 10 MPa or more, and the compressive breaking strain is 50% or more. Rubber material.
- (6) The decomposable rubber member for downhole tools according to (5), wherein the surface hardness is in the range of A60 to D80.
- the decomposition accelerator is a plasticizer.
- the decomposition accelerator contains at least one selected from the group consisting of organic acids, inorganic acids, organic acid esters, inorganic acid esters, and acid anhydrides Degradable rubber material for hall tools.
- the decomposable rubber member for downhole tools according to any one of (1) to (8), which contains at least one selected from the above.
- Degradable rubber is composed of urethane rubber, natural rubber, isoprene rubber, ethylene propylene rubber, butyl rubber, styrene rubber, acrylic rubber, aliphatic polyester rubber, chloroprene rubber, polyester thermoplastic elastomer, and polyamide thermoplastic elastomer.
- a downhole tool comprising the decomposable rubber member for downhole tools according to any one of (1) to (23), preferably (25) for drilling a well
- the downhole tool according to (24), which is a plug is provided.
- a well drilling method is provided.
- the following (29) to (32) well drilling methods are provided as specific embodiments of the invention.
- (29) After sealing a wellbore using the downhole tool including the decomposable rubber member for a downhole tool according to any one of (1) to (23), the downhole tool is formed in the wellbore.
- a well drilling method wherein a degradable rubber member is disassembled.
- (30) Using a downhole tool comprising the decomposable rubber member for a downhole tool according to any one of the above (1) to (23) and further comprising another downhole tool member containing a degradable material, A well excavation method, wherein after the well hole is sealed, the decomposable rubber member for the downhole tool is decomposed in the well hole.
- the decomposability for downhaul tools is formed from a rubber material containing 0.1 to 20 parts by mass of a decomposition accelerator with respect to 100 parts by mass of the degradable rubber.
- Being a rubber member makes it possible to reliably seal the fluid and facilitate well treatment while the mining conditions become diverse, and to release the seal and secure the flow path in a desired period.
- the cost of well drilling can be applied to degradable seal members that can be designed as desired, and degradable protective members that can be designed to protect and easily remove sensors and flow paths, etc.
- a decomposable rubber member for a downhole tool that can be reduced or shortened is provided.
- a downhole tool including the member and a well excavation method are provided. Offer An effect that is can be attained.
- the degradable rubber member for downhole tool according to the first aspect of the present invention is formed from a rubber material containing a predetermined amount of a decomposition accelerator in degradable rubber. .
- the decomposable rubber member for downhole tools of the present invention can be applied to a degradable seal member for downhole tools and a degradable protective member for downhole tools, thereby reducing the cost of well drilling and shortening the process. There is an effect.
- the decomposable rubber member for a downhole tool of the present invention will be described mainly showing a specific example of the decomposable seal member for a downhole tool. 1.
- Degradable rubber Decomposable rubber for forming a decomposable sealing member for a downhole tool (degradable rubber member) of the present invention containing a predetermined amount of a decomposing accelerator has been conventionally used as a decomposable rubber for a downhaul tool.
- the decomposable rubber that has been used to form the adhesive seal member can be used.
- the degradable rubber contained in the rubber material forming the decomposable sealing member for downhole tools may be used alone or in combination of two or more degradable rubbers.
- the degradability of the degradable rubber contained in the rubber material forming the decomposable rubber member (degradable seal member) for downhole tools is, for example, by microorganisms in the soil where well treatment such as fracturing is performed Biodegradable to be decomposed, hydrolyzable to be decomposed by a solvent such as a fracturing fluid, especially water, and further by an acid or alkali as desired, especially hydrolyzable to be decomposed by water at a predetermined temperature or more, and other
- the strength inherent to rubber decreases due to a decrease in the degree of polymerization and the like, resulting in brittleness.
- the sealing member (degradable rubber member) for the downhole tool easily collapses and loses its shape (disintegrating property).
- degradable rubber The degradable rubber contained in the rubber material forming the degradable seal member (degradable rubber member) for the downhole tool of the present invention is urethane rubber, natural rubber, isoprene rubber, ethylene propylene rubber, butyl rubber, styrene rubber, acrylic Examples include degradable rubber containing at least one selected from the group consisting of rubber, aliphatic polyester rubber, chloroprene rubber, polyester thermoplastic elastomer, and polyamide thermoplastic elastomer.
- a predetermined amount of a decomposition accelerator described later is not necessarily degradable rubber, that is, a nondegradable rubber having a compressive stress reduction rate at 150 ° C. for 24 hours of less than 5%, which will be described later.
- a decomposable sealing member for downhole tools may be formed.
- the so-called nondegradable rubber also corresponds to the degradable rubber of the present invention.
- degradable rubber is a hydrolyzable functional group (for example, urethane group, ester group, amide group, carboxyl group, hydroxyl group, silyl group, acid anhydride, acid halide, etc.
- Decomposable rubber containing a rubber having is also preferred.
- “having a functional group” means having as a bond that forms the main chain of the rubber molecule, or having as a side chain of the rubber molecule that becomes a crosslinking point, for example.
- a particularly preferred degradable rubber is one containing a urethane rubber having a hydrolyzable urethane bond.
- the decomposable rubber preferably contains a polyester-based thermoplastic elastomer or a polyamide-based thermoplastic elastomer.
- the urethane rubber (sometimes referred to as “urethane elastomer”) that is particularly preferably used as the degradable rubber contained in the rubber material forming the degradable seal member (degradable rubber member) for the downhole tool of the present invention.
- a rubber material having a urethane bond (—NH—CO—O—) in the molecule is usually obtained by condensing an isocyanate compound and a compound having a hydroxyl group.
- the isocyanate compound aromatic (which may have a plurality of aromatic rings), aliphatic, and alicyclic di, tri, and tetra polyisocyanates, or mixtures thereof are used.
- ester type urethane rubber As a compound having a hydroxyl group, a polyester type urethane rubber having an ester bond in its main chain (hereinafter sometimes referred to as “ester type urethane rubber”) and a polyether type urethane rubber having an ether bond in its main chain (hereinafter, referred to as “ester type urethane rubber”).
- ester type urethane rubber is preferable because it is easier to control degradability and disintegration.
- Urethane rubber is an elastic body that has both the elasticity (softness) of synthetic rubber and the rigidity (hardness) of plastic. Generally, it has excellent wear resistance, chemical resistance, oil resistance, high mechanical strength, and load resistance. Is large, and is known to have high elasticity and high energy absorption.
- urethane rubber i) kneading (millable) type: can be molded by the same processing method as general rubber, ii) thermoplastic type: can be molded by the same processing method as thermoplastic resin, and iii) due to the difference in molding method Casting type:
- the type classification is that it can be molded by a method of thermosetting using a liquid raw material, but any type of urethane rubber that forms the degradable sealing member for downhole tools of the present invention Can also be used.
- iii) molding technology of cast type urethane rubber is usually divided into two methods, a one-shot method and a prepolymer method.
- the one-shot method is a method in which all reactant raw materials are mixed and stirred in a reaction vessel, and then cast and released after completing the reaction by primary heat treatment, followed by secondary heat treatment.
- the prepolymer method has two steps: a step of reacting polyol and diisocyanate in advance to synthesize a prepolymer, and a step of reacting the prepolymer with other insufficient raw materials to finally form urethane rubber.
- the polyester-based thermoplastic elastomer preferably used as the decomposable rubber contained in the rubber material forming the degradable seal member (degradable rubber member) for the downhole tool of the present invention is mainly composed of a polyester block copolymer. This is an elastomer.
- a block copolymer of a hard segment made of polyester and a soft segment made of polyether there is a block copolymer of a hard segment made of polyester and a soft segment made of polyether.
- the hard segment aromatic polyester or aliphatic polyester, more specifically polyethylene terephthalate, polybutylene terephthalate.
- Polyethylene naphthalate, polybutylene naphthalate, polyhydroxyalkanoic acid and the like, and examples of the soft segment include polyethers such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol.
- a block copolymer comprising a hard segment and a soft segment made of polyester
- the hard segment include aromatic polyester, more specifically polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like.
- the soft segment include aliphatic polyesters having a lower elastic modulus than the hard segment, such as polyhydroxyalkanoic acid having an alkyl chain length of 2 or more.
- polyester-based thermoplastic elastomer having desired physical properties can be obtained by a combination with various compounding agents.
- Polyester-based thermoplastic elastomers have both plastic and rubber properties, and can be molded in a variety of ways such as injection molding, extrusion molding, blow molding, etc. It is easy to decompose and disintegrate.
- the polyamide-based thermoplastic elastomer preferably used as the decomposable rubber contained in the rubber material forming the decomposable seal member (degradable rubber member) for the downhole tool of the present invention includes a hard segment made of polyamide, a polyether, And / or a block copolymer with a soft segment made of polyester.
- examples of the hard segment include aliphatic polyamide, more specifically, nylon 6, nylon 11, and nylon 12.
- examples of the soft segment include polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. And the like. These hard segments and soft segments can be adjusted in the types of hard segments and soft segments or their ratios so as to match the desired physical properties of the elastomer, in particular the desired degradation and mechanical properties.
- a polyamide-based thermoplastic elastomer having desired physical properties can be obtained by a combination with various compounding agents as necessary.
- Polyamide-based thermoplastic elastomers have intermediate properties between rubber and plastic, can be molded by various methods such as injection molding, extrusion molding, blow molding, etc. It has the property of causing hydrolysis under high pressure, resulting in easy decomposition and easy disintegration.
- nitrile rubber and hydrogenated nitrile rubber which are widely used for downhole tools, are, for example, 150 ° C. 24 hours compressive stress reduction rate
- the degradable rubber contained in the rubber material forming the decomposable sealing member (degradable rubber member) for the downhole tool of the present invention is also considered from the viewpoint that it is difficult to make it within a predetermined range. Is not applicable.
- the decomposition accelerator contained in the degradable seal member (degradable rubber member) for the downhole tool of the present invention is decomposable in a downhole environment where the decomposable seal member for a downhole tool is used.
- the decomposition accelerator is a compounding agent having a function of cutting the bond of the main chain of the rubber molecule of the degradable rubber or a function of plasticizing the degradable rubber. It is preferred that there are, therefore, degradation accelerators preferably include acidic substances and plasticizers.
- the decomposition accelerator preferably contains at least one selected from the group consisting of organic acids, inorganic acids, organic acid esters, inorganic acid esters, and acid anhydrides.
- an acidic substance can be mentioned as a preferable decomposition accelerator.
- the acidic substance breaks down the rubber member by breaking the bond of the main chain of the rubber molecule of the decomposable rubber contained in the rubber member forming the degradable seal member (degradable rubber member) for the downhole tool.
- disassembly of the decomposable sealing member for the downhole tool is promoted. That is, when the degradable sealing member for downhole tools is formed from a rubber material that is a degradable rubber containing an acidic substance, the acidic substance is usually dispersed homogeneously inside the degradable rubber.
- the degradable sealing member for a downhole tool formed from a rubber material is water (which may contain an acidic substance). It is presumed that the decomposition of the degradable rubber proceeds at a higher rate compared to the case where the decomposition proceeds from the surface of the sealing member as in the case of immersion in the surface.
- the acidic substance may be a narrowly defined acidic substance such as an acid, or an acid-generating substance that hydrolyzes to generate an acid when immersed in water under some conditions, for example.
- Acid generators include acids such as organic acids and inorganic acids, hydrolyzable acid derivatives such as oxycarboxylic acid dimers, trimers, oligomers or polymers, and high reactivity.
- Derivatives of organic acids for example, sulfonic acid derivatives such as sulfonic acid esters (corresponding to organic acid esters), sulfonamides, acid anhydrides and the like, acid generators known per se as acid precursors, preferably organic acid esters, Examples include inorganic acid esters and acid anhydrides.
- the acidic substance is a period from the rubber material, which is a degradable rubber containing a predetermined amount of acidic substance, to the formation of a degradable seal member for downhole tools (during polymerization of degradable rubber, melt kneading or melt molding, etc. ) Is not decomposed or volatilized and does not disappear.
- saturated fatty acids having about 8 to 20 carbon atoms such as lauric acid, glycolic acid, lactic acid, phosphoric acid, glycolide, glycolic acid oligomer, polyglycolic acid (PGA), lactide, lactic acid oligomer, polylactic acid (PLA)
- Oxycarboxylic acids such as ⁇ -caprolactone or derivatives thereof, sulfonic acid derivatives such as methyl p-toluenesulfonate (MPTS), o / p-toluenesulfonamide, N-butylbenzenesulfonamide, 3, 3 ′, 4,
- acid anhydrides such as 4′-benzophenone tetracarboxylic dianhydride (BTDA).
- the decomposition accelerator contains at least one selected from the group consisting of glycolide, lactide, ⁇ -caprolactone, PGA, PLA, MPTS and BTDA.
- the addition is usually performed by injecting the acidic substance into the prepolymer.
- the prepolymer is preheated to a temperature of about 80 ° C., a predetermined amount of acidic substance is added while stirring, the mixture is stirred for about 3 to 5 minutes, and then the prepolymer is defoamed and the temperature is adjusted. (Alternatively, the temperature may be adjusted after defoaming and an acidic substance may be added.)
- a curing agent After adding a curing agent, it is poured into a temperature-controlled mold to complete primary vulcanization (primary heat treatment).
- secondary vulcanization secondary heat treatment
- the primary vulcanization usually takes about 30 to 60 minutes until the shape can be maintained after demolding, for example, in the case of cast-type urethane rubber.
- an acidic substance is added to the prepolymer, depending on the type of acidic substance, (1) one that does not change from normal vulcanization time, (2) one that is shorter than normal vulcanization time, (3) normal vulcanization time It has been found that there are those that require a longer time than (4) those in which the primary vulcanization does not proceed (does not cure).
- bond breakage by acid occurs in parallel, the progress of primary vulcanization may be suppressed (not cured).
- an acid such as glycolic acid causes bond breakage during the progress of the curing reaction or deactivates the curing agent by reaction with the curing agent. If it is contained in an amount of about 5 parts by mass, the curing reaction may not proceed. Therefore, as the acidic substance, for example, those capable of releasing acid over time in the process of using a degradable rubber member for downhole tools, for example, glycolide, lactide, ⁇ -caprolactone, PGA, PLA, Acid generators such as MPTS or BTDA are preferred.
- the acidic substance is in a state of compatibility with granular materials ("granular" May be dispersed).
- granular May be dispersed
- glycolide, lactide, glycolic acid, MPTS, etc. are often in a compatible state
- PGA, PLA, BTDA, etc. are granular because of their melting points. Is often dispersed.
- lauric acid sometimes disperses in a compatible state and granular form depending on temperature conditions and the like, and may bleed out from the molded product.
- the effect of promoting the decomposition of the degradable rubber is usually larger in the case of being in a compatible state, but it is granular or powdery with an appropriate dispersion diameter. Even if it is dispersed by the above method, there is no problem in use as long as the decomposable rubber member can be decomposed into a fine powder state.
- the content of the acidic substance that is a decomposition accelerator with respect to 100 parts by mass of the degradable rubber is not particularly limited, but is usually 0.1 to 20 parts by mass, often 0.3 to 15 parts by mass, in most cases It has a decomposition promoting effect on degradable rubber in the range of 0.5 to 10 parts by mass.
- the content of the acid such as glycolic acid is a small amount of less than 5 parts by mass so as not to cause bond breakage or deactivation of the curing agent during the progress of the curing reaction. Less than, more preferably less than 2 parts by mass.
- a plasticizer may be mentioned as a preferable decomposition accelerator.
- the plasticizer has the function of plasticizing the degradable rubber (torque reduction, softening, etc.) contained in the rubber member forming the degradable seal member (degradable rubber member) for downhole tools.
- the decomposition of the decomposable rubber proceeds at a higher rate compared to the case where the decomposition proceeds from the surface of the degradable sealing member (degradable rubber member) for the downhole tool.
- the plasticizer include dibutyl phthalate, diisononyl phthalate, dioctyl phthalate, dioctyl adipate, diisononyl adipate, dibutyl sebacate and the like.
- the type of plasticizer is determined by the combination with the degradable rubber.
- the content of the plasticizer with respect to 100 parts by mass of the degradable rubber is not particularly limited, and the optimum range in which the decomposition promoting effect can be exhibited can be determined by the combination of the plasticizer and the degradable rubber described above. 1 to 20 parts by mass, and in most cases 0.3 to 15 parts by mass, and in most cases 0.5 to 10 parts by mass, it has a decomposition promoting effect on degradable rubber.
- the decomposition accelerator in addition to the acidic substances and plasticizers mentioned above, those that have the effect of promoting the decomposition of the degradable rubber, particularly hydrolysis, can be used.
- the decomposition accelerator may be a single compound alone, may contain two or more compounds, and may contain, for example, an acidic substance and a plasticizer. Further, as described above for the acidic substance, the content of the decomposition accelerator may be compatible or granular, but from a rubber material, a decomposable sealing member for a downhole tool (degradable rubber member) It is necessary that it does not disappear due to decomposition or volatilization until it is formed (during polymerization of degradable rubber, melt kneading or melt molding).
- the content of the decomposition accelerator can be selected in the optimum range depending on the combination of the decomposition accelerator and the decomposable rubber, but is usually 0.1 to 20 parts by mass with respect to 100 parts by mass of the decomposable rubber.
- the decomposition promoting effect on degradable rubber is in the range of 0.3 to 15 parts by mass, and in most cases in the range of 0.5 to 10 parts by mass. If the content of the decomposition accelerator is too small, the decomposition promoting effect on the degradable rubber is insufficient, and there is a possibility that the decomposable sealing member for the downhole tool cannot be disassembled and the seal cannot be released within the desired period. Drilling cost reduction and process shortening may be impaired.
- the degradable sealing member for downhole tools of the present invention is formed from a rubber material containing 0.1 to 20 parts by mass of a decomposition accelerator with respect to 100 parts by mass of the degradable rubber, so that the decomposable rubber can be decomposed.
- the release of the seal by the decomposable sealing member for the downhole tool which is performed after completion of the well treatment or after completion of the well drilling, is performed at a lower temperature and / or in a shorter time. Therefore, under a variety of mining conditions, the seal can be released in a desired period, and well drilling costs can be reduced and the process can be shortened. Furthermore, since the degradable rubber contained in the rubber material forming the decomposable seal member for downhole tools can be decomposed not from the surface of the seal member, but also from the inside, it is possible to disassemble the downhole tool after releasing the seal.
- the decomposable sealing member (degradable rubber member) for downhole tools of the present invention is formed from a rubber material containing 0.1 to 20 parts by mass of a decomposition accelerator with respect to 100 parts by mass of degradable rubber.
- the rubber material forming the degradable seal member (degradable rubber member) for the downhole tool is not limited to the degradable rubber and the predetermined amount of the decomposition accelerator, and further within the range not impairing the object of the present invention. Contains other additives (degradable polymers other than degradable rubber, non-degradable resins and rubbers), various additives such as stabilizers, colorants, and reinforcing materials as other compounding ingredients can do.
- the rubber material forming the decomposable seal member (decomposable rubber member) for the downhole tool may contain a reinforcing material.
- a rubber material containing 0.1 to 20 parts by mass of a decomposition accelerator with respect to 100 parts by mass of degradable rubber contains a degradable polymer other than degradable rubber, a resin or rubber having no decomposability.
- the decomposition accelerator contained in the rubber material is prepared so as to be contained at a ratio of 0.1 to 20 parts by mass with respect to 100 parts by mass of the decomposable rubber.
- Reinforcement material As the reinforcing material, it is possible to use a material that has been conventionally used as a reinforcing material such as a resin material for the purpose of improving mechanical strength and heat resistance, such as a fibrous reinforcing material or a granular or powdered reinforcing material. Can be used.
- the reinforcing material can be contained in an amount of usually 150 parts by mass or less, preferably 10 to 100 parts by mass with respect to 100 parts by mass of the degradable rubber. If the rubber material forming the decomposable sealing member (degradable rubber member) for the downhole tool of the present invention contains a reinforcing material, the downhole environment is close to the melting point (melt softening point) of the degradable rubber. Even in the environment, it may be possible to perform sealing (protection for degradable rubber members) for a period required for processing.
- fibrous reinforcing materials include glass fibers, carbon fibers, asbestos fibers, silica fibers, alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, potassium titanate fibers, and the like; stainless steel, aluminum Metal fiber materials such as titanium, steel and brass; high melting point organic fiber materials such as aramid fiber, kenaf fiber, polyamide, fluororesin, polyester resin and acrylic resin; and the like.
- fibrous reinforcing material short fibers having a length of 10 mm or less, more preferably 1 to 6 mm, and further preferably 1.5 to 4 mm are preferable, inorganic fibrous materials are preferably used, and glass fibers are particularly preferable. preferable.
- Granular or powdery reinforcing materials include mica, silica, talc, alumina, kaolin, calcium sulfate, calcium carbonate, titanium oxide, ferrite, clay, glass powder (milled fiber, etc.), zinc oxide, nickel carbonate, iron oxide, quartz Powder, magnesium carbonate, barium sulfate or the like can be used.
- the reinforcing materials can be used alone or in combination of two or more.
- the reinforcing material may be treated with a sizing agent or a surface treatment agent as necessary.
- degradable polymers other than degradable rubbers or resins or rubbers not having degradability may be used as other resins (degradable polymers other than degradable rubbers or resins or rubbers not having degradability may be used) that can be further contained as other blending components as long as the object of the present invention is not impaired. If it is desired to promote the loss of the sealing function, degradable polymers other than degradable rubbers such as polyglycolic acid, stereocomplex polylactic acid, polybutylene succinate, polybutylene adipate / It may contain terephthalate, polybutylene succinate / adipate, and the like.
- thermoplastic resins such as aromatic polyester (polyethylene terephthalate, etc.) and polystyrene; nitrile rubber, hydrogenated nitrile rubber, ethylene Examples thereof include non-degradable rubber such as propylene / diene terpolymer (EPDM). If the rubber material contains other resins (degradable polymers other than degradable rubbers or non-degradable resins or rubbers), the content of other resins is the degradable seal for downhole tools.
- thermoplastic resins such as aromatic polyester (polyethylene terephthalate, etc.) and polystyrene; nitrile rubber, hydrogenated nitrile rubber, ethylene Examples thereof include non-degradable rubber such as propylene / diene terpolymer (EPDM). If the rubber material contains other resins (degradable polymers other than degradable rubbers or non-degradable resins or rubbers), the content of other resins is the degradable seal for downhole tools.
- Decomposable rubber member for downhaul tool Down of the degradable seal member for downhaul tool of the present invention formed from a rubber material containing 0.1 to 20 parts by mass of decomposition accelerator with respect to 100 parts by mass of degradable rubber
- the degradable rubber member for hall tools can have the same configuration, structure, and shape as the degradable sealing member for downhole tools and the degradable protective member for downhole tools that have been used in the past.
- the degradable rubber member for downhole tools of the present invention is further reduced in mass after immersion for 24 hours in water at a temperature of 150 ° C. from the viewpoint of reliably exhibiting degradability in a downhole environment.
- the rate (hereinafter sometimes referred to as “150 ° C. 24-hour mass reduction rate”) is preferably 5% or more.
- the mass reduction rate is set to 100%.
- the decomposable rubber member for downhole tools has a mass reduction rate of 5% or more at 150 ° C for 24 hours, so the downhole environment (the temperature is about 60 ° C to 200 ° C associated with diversification of depth, etc. In recent years, there is a further downhole environment at a low temperature of about 25 to 40 ° C.), and within a few hours to a few weeks, the decomposability for downhole tools formed from a rubber material containing a predetermined amount of decomposition accelerator
- the rubber member (decomposable seal member) is decomposed or collapsed, and more preferably disappears (in the present invention, it may be collectively referred to as “decompose”), so that the degradable rubber member for downhole tools (degradable) Since the sealing function by the sealing member) is lost, it is possible to contribute to cost reduction and process shortening for well drilling.
- Decomposable rubber members for downhole tools have various types of seal function function maintenance time and function loss time depending on the environment such as various downhole temperatures and the processes performed in the environment.
- the degradable rubber member (degradable seal member) for the downhole tool of the present invention preferably has a mass reduction rate of 150% at 24 ° C. for 5 hours or more, more preferably 10% or more, still more preferably. Is not less than 50%, particularly preferably not less than 80%, most preferably not less than 90%, desirably 100% which is the upper limit value, and in combination with the function of the decomposition accelerator, for example, a temperature of 177 ° C.
- the seal function can be exhibited for a certain period of time, and then the seal function can be lost to release the seal.
- the factor controlling the degree of mass loss at 150 ° C. for 24 hours of the degradable rubber member for downhole tools and the degree to which it can be controlled vary depending on the type of degradable rubber contained in the rubber material forming the degradable rubber member for downhole tools.
- the decomposition rate by adjusting the degree of vulcanization, that is, by controlling the degree of crosslinking between molecular chains, by controlling the decomposition rate by changing the vulcanization method or by changing the type and ratio of the crosslinking agent, and by the hardness
- the speed in general, increasing the hardness suppresses decomposition and decreasing the hardness accelerates decomposition
- the type and amount of the compounding agent and filler such as a hydrolysis inhibitor in the rubber material
- Decomposition rate can be controlled by controlling the decomposition rate and changing molding conditions and curing conditions.
- the decomposable rubber member for downhole tools of the present invention has a 50% strain compressive stress after immersion in water at a temperature of 150 ° C. for 24 hours from the viewpoint of reliably exhibiting degradability in a downhole environment. It is preferable that the reduction rate with respect to% strain compressive stress (hereinafter sometimes referred to as “150 ° C. 24-hour compressive stress reduction rate”) is 5% or more.
- decrease rate of the decomposable rubber member for downhaul tools is as follows.
- a sample with a predetermined shape (a sample cut into 5 mm thickness, length, and width) is immersed in 400 mL of water (such as deionized water) at a temperature of 150 ° C., taken out after 24 hours,
- water such as deionized water
- the compressive stress is measured at room temperature, and the compressive stress at 50% compressive strain (unit: MPa, hereinafter referred to as “50% strain compressive stress”) is determined.
- a reduction rate unit:%) relative to the initial compressive stress is calculated.
- the reduction rate is set to 100%.
- the initial compressive stress of the decomposable rubber member for downhole tools of the present invention that is, 50% strain compressive stress before immersion in water at a temperature of 150 ° C., fracturing, etc. in the downhole in the deep underground
- the period required to perform the well treatment including the loading / transfer of the plug to a predetermined position, the blocking of the downhole by the decomposable rubber member for the downhole tool, and the preparation and implementation of drilling or fracturing
- the initial 50% strain compressive stress of the decomposable rubber member for downhole tools is not particularly limited, but is usually 200 MPa or less, and in many cases 150 MPa or less, from the viewpoint of handleability and decomposability (or disintegration). Is used.
- the decomposable rubber member for downhole tools has a reduction rate of compressive stress of 150% at 24 ° C for 5% or more, so the downhole environment (at a temperature of about 60 ° C to 200 ° C accompanying the diversification of depth) In recent years, there is also a low-temperature downhole environment of about 25 to 40 ° C.) in a desired period of several hours to several weeks, and is formed from a rubber material containing a predetermined amount of a decomposition accelerator. Since the decomposable rubber member for the downhole tool (degradable seal member) is decomposed or collapsed, the sealing function by the degradable rubber member for the downhole tool (degradable seal member) is lost.
- Decomposable rubber members for downhole tools have various types of seal function function maintenance time and function loss time depending on the environment such as various downhole temperatures and the processes performed in the environment.
- the degradable rubber member (degradable seal member) for downhole tools of the present invention preferably has a compression stress reduction rate of 150 ° C.
- the sealing function is exhibited for a certain period of time, and then the sealing function is lost. It can be assumed to have the characteristics of releasing the seal.
- the factor controlling the degree of compressive stress reduction at 150 ° C. for 24 hours of the degradable rubber member for downhole tools and the degree of control are the same as described above, and the rubber material forming the decomposable rubber member for downhole tools
- adjusting the degree of vulcanization that is, controlling the decomposition rate by controlling the degree of crosslinking between molecular chains, changing the vulcanization method, and the type and ratio of the crosslinking agent Control of decomposition rate by changing the hardness, control of decomposition rate by hardness (generally, increasing the hardness suppresses decomposition and decreasing the hardness promotes decomposition), blending of hydrolysis inhibitors in rubber materials, etc.
- the decomposition rate can be controlled by adjusting the type and amount of the agent and filler, and the decomposition rate can be controlled by changing molding conditions and curing conditions.
- the upper limit of the compressive stress reduction rate at 150 ° C. for 24 hours of the degradable rubber member for downhole tools is 100%.
- the decomposable rubber member for downhaul tools of the present invention has a compressive stress reduction rate of 150% at 24 ° C. for 100% as required, and various temperatures such as a temperature of 93 ° C., 66 ° C., 40 ° C. or 25 ° C.
- the reduction rate of 50% strain compressive stress after immersion for 24 hours in 50% strain compressive stress before immersion is, for example, 50% or less, 30% or less, 10% or less, and further less than 5%.
- the degradable rubber member for downhole tools of the present invention is further reduced in mass after immersion for 72 hours in water at a temperature of 150 ° C. from the viewpoint of reliably exhibiting degradability in a downhole environment.
- the rate (hereinafter sometimes referred to as “150 ° C. 72 hour mass reduction rate”) is preferably 5 to 100%.
- the 150 ° C. 72 hour mass reduction rate of the decomposable rubber member for down hole tools is the same as described above for the 150 ° C. 24 hour mass reduction rate, and for down hole tools cut into 20 mm thickness, length, and width.
- a sample of a degradable rubber member is immersed in 400 mL of water (deionized water or the like) at a temperature of 150 ° C. and taken out after 72 hours and before being immersed in water at a temperature of 150 ° C. in advance. It is calculated by comparing the measured mass (initial mass) of the sample.
- the decomposable rubber member for downhole tools has a mass reduction rate of 5 to 100% at 150 ° C for 72 hours, so the downhole environment (at a temperature of about 60 ° C to 200 ° C associated with diversification of depth, etc.) In recent years, there is also a downhole environment at a low temperature of about 25 to 40 ° C.), and within a few hours to a few weeks, the decomposition for downhole tools formed from a rubber material containing a predetermined amount of decomposition accelerator
- the decomposable rubber member (decomposable seal member) is decomposed or disintegrated, and more preferably disappears (in the present invention, it may be collectively referred to as “decompose”), so that the decomposable rubber member for the downhole tool (decomposed) Since the sealing function by the conductive seal member) is lost, it is possible to contribute to cost reduction and process shortening for well drilling.
- Decomposable rubber members for downhole tools have various types of seal function function maintenance time and function loss time depending on the environment such as various downhole temperatures and the processes performed in the environment.
- the degradable rubber member (degradable seal member) for downhole tools of the present invention has a mass reduction rate of 150 ° C. for 72 hours, more preferably 10 to 100%, still more preferably 50 to 100%, particularly preferably. 80-100%, most preferably 90-100%, coupled with the function of the decomposition accelerator described later, for example, a temperature of 177 ° C., 163 ° C., 149 ° C., 121 ° C., 93 ° C., 80 ° C.
- the decomposable rubber member for downhole tools according to the present invention has a tensile fracture strain at a temperature of 66 ° C. (hereinafter, also referred to as “66 ° C. tensile fracture strain”) of 50% or more, if desired.
- the strength of the decomposable rubber member for downhole tools is maintained during the period required to perform well processing such as downhole blocking (protection of sensors etc. for degradable protective members; the same applies hereinafter). This is preferable because it can be continued reliably. That is, when a well hole is closed (seal) using a decomposable rubber member for a downhole tool, the decomposable rubber member for the downhole tool has the shape of the downhole tool and the shape of the downhole (casing of the casing).
- Decomposable rubber member for downhaul tools because there is no risk of breaking even if it is deformed so as to be surely engaged with the shape), or specifically deformed while receiving a large tensile force (and compressive force)
- the contact area between the casing and the casing is increased, and the blockage is ensured.
- a large tensile force (and compressive force) may be applied. There is an effect that the seal is not easily broken.
- the 66 ° C. tensile breaking strain is measured at a temperature of 66 ° C. in accordance with ISO 37 (JIS K6251). The 66 ° C.
- the decomposable rubber member for a downhole tool of the present invention has a 70% strain compressive stress (hereinafter, also referred to as “66 ° C. compressive stress”) at a temperature of 66 ° C. of 10 MPa or more as desired.
- the strength of the decomposable rubber member for downhole tools is maintained during the period required for performing well processing such as the above, and the blockage of the downhole can be continued more reliably. That is, when a well hole is closed (seal) using a decomposable rubber member for a downhole tool, the decomposable rubber member for the downhole tool has the shape of the downhole tool and the shape of the downhole (casing of the casing). There is no risk of breakage even if it is deformed so as to be surely engaged with the shape), specifically, while receiving a large compressive force (and tension). The contact area with the casing is increased, and blockage is ensured.
- the 66 ° C. compressive stress is measured at a temperature of 66 ° C. according to ISO 14126 (JIS K7018). It represents the maximum stress value up to.
- the 66 ° C. compressive stress is more preferably 20 MPa or more, and further preferably 30 MPa or more.
- the 66 ° C. compressive stress has no particular upper limit, but is usually 200 MPa or less, and in many cases 150 MPa or less.
- the decomposable rubber member for downhole tools of the present invention has a compression fracture strain at a temperature of 66 ° C. (hereinafter sometimes referred to as “66 ° C. compression fracture strain”) of 50% or more, as desired.
- 66 ° C. compression fracture strain is measured at a temperature of 66 ° C. in accordance with ISO14126.
- the 66 ° C. compression breaking strain is more preferably 60% or more, and still more preferably 70% or more. The upper limit of the 66 ° C.
- the degradable rubber member for downhole tools of the present invention has a surface hardness from the viewpoint of a sealing function. A range of A60 to D80 is preferable.
- the surface hardness of the rubber material forming the decomposable rubber member for a downhole tool may be a durometer hardness type A (hereinafter referred to as “surface hardness A” or simply “hardness A”) measured in accordance with ISO7619.
- type D (hereinafter, sometimes referred to as “surface hardness D” or simply “hardness D”).
- the durometer hardness there are type A for medium hardness suitable for general rubber, type D for high hardness suitable for hard rubber, etc., and type E for low hardness suitable for sponge etc. (for example, The hardness A100 generally corresponds to a hardness of about D60.
- the rubber material forming the decomposable rubber member for downhole tools of the present invention has a hardness in the range of A60 to D80, and further adjusts the structure of the rubber member and the like as desired, thereby enabling high pressure such as fracturing. A well hole can be sealed against fluid pressurization.
- the surface hardness of the rubber material forming the decomposable rubber member for downhole tools is more preferably in the range of surface hardness A65 to D78, still more preferably surface hardness A70 to D75.
- the decomposable rubber member for downhole tools of the present invention is further stable in a dry environment, if desired, 50% strain compressive stress after being immersed in water at a temperature of 23 ° C. for 6 hours, and 50% after being immersed for 1 hour.
- the period required to perform well treatment such as fracturing because the rate of reduction with respect to strain compression stress (hereinafter sometimes referred to as “23 ° C. compression stress reduction rate”) is less than 5%.
- the strength of the degradable rubber member is maintained and the downhole can be blocked more reliably.
- the downhole blockage (protective function of the sensor, etc. in the protective member) is lost in an unexpectedly short time. There is no.
- the decomposable rubber member for downhole tools is stable in a dry environment, the downhaul tool provided with the decomposable rubber member for downhole tools of the present invention is arranged in a wellbore, such as fracturing.
- the sealing function (protective function in the protective member) is not lost in the stage before the well treatment is performed.
- compressive stress reduction rate of the decomposable rubber member for downhole tools is the same as the method for measuring the 150 ° C. 24-hour compressive stress reduction rate described above. Instead, it can be measured by immersing in water at a temperature of 23 ° C. for a required time.
- the 23 ° C. compressive stress reduction rate is more preferably less than 4%, and even more preferably less than 3%.
- the lower limit of the 23 ° C. compressive stress reduction rate is 0%.
- “stable in a dry environment” means a reduction in compressive stress for 168 hours (7 days) or more in an environment of a temperature of 23 ° C. and a relative humidity of 50%. It means that does not occur.
- the degradable rubber member for downhole tools of the present invention may further have a compressive stress ratio of 70% compressive stress to a compressive stress of 5% compressive strain at a temperature of 66 ° C. (hereinafter referred to as “66 ° C. compressive stress ratio”). ) Is more than 5 times, the strength of the decomposable rubber member for downhole tools is maintained during the period required for well treatment such as fracturing, and the blockage of the downhole is more reliably performed. It is preferable because it can be continued.
- the initial compressive strain of the decomposable rubber member for downhole tools is small (it is easy to deform). It can be deformed to securely engage with the shape of the hole tool and the shape of the down hole (casing shape), and when the deformation is performed while receiving a large compressive force (and tensile force), the amount of deformation is
- the stress of the rubber member rises greatly in a large region, for example, the rubber member at the contact portion between the rubber member and the casing has a high compressive stress (and tensile force), and thus a seal such as fracturing is necessary.
- the 66 ° C. compressive stress ratio is measured at a temperature of 66 ° C. in accordance with ISO 14126 (JIS K7018).
- the 66 ° C. compressive stress ratio is more preferably 8 times or more, and still more preferably 10 times or more.
- the 66 ° C. compressive stress ratio has no particular upper limit, but is usually 200 times or less, and often 150 times or less. Note that the decomposable rubber member for downhole tools of the present invention having a 66 ° C.
- the compressive stress ratio of 5 times or more often has a compressive strain of 5 even at other temperatures, for example, a temperature range from room temperature to 177 ° C. If the ratio of the compressive stress at 70% compressive strain to the compressive stress at% is 5 times or more, the sealing function and the like can be achieved in the above wide temperature range, which is more desirable. However, even in a part of the above temperature range, for example, at a temperature of 149 ° C., even the decomposable rubber member for downhole tools in which the compression stress ratio is less than 5 times, the 66 ° C. compression stress ratio is 5 times or more. If there is, it is a decomposable rubber member for downhole tools that is practical.
- the degradable seal member (degradable rubber member) for downhole tools of the present invention has a flexural modulus at a temperature of 23 ° C. of 0, depending on necessity, from the viewpoint of reliably exerting a sealing function in various downhole environments. It can be in the range of 005-10 GPa. If the bending elastic modulus at a temperature of 23 ° C. of the degradable seal member for downhole tools of the present invention is in the range of 0.005 to 10 GPa, the downhole environment, for example, temperatures of 177 ° C., 163 ° C., 149 ° C., 121 ° C., If a well is blocked in an environment such as 93 ° C., 80 ° C.
- the downhole The bending elastic modulus of the decomposable sealing member for downhole tools is moderately reduced in the environment, so the degradable sealing member for the downhaul tool (degradable rubber member) ensures that the shape of the downhaul tool and the casing It can be deformed to engage. Accordingly, the contact area between the downhole tool decomposable sealing member and the casing is increased, and the blockage is ensured.
- the flexural modulus at a temperature of 23 ° C. is measured according to JIS 7113 (corresponding to ISO 178).
- the bending elastic modulus at a temperature of 23 ° C. of the decomposable sealing member for a downhole tool is preferably 9 GPa or less, from the viewpoint of easy deformation that ensures the sealing function in the downhole environment. More preferably, it is 8 GPa or less, More preferably, it is 7 GPa or less, and it is effective especially in the sealing member whose thickness exceeds 5 mm. If the bending elastic modulus at a temperature of 23 ° C. of the decomposable sealing member for downhole tools is too small, the seal may be destroyed by deformation when a high fluid pressure is applied. Therefore, it is preferably 0.008 GPa.
- the decomposable sealing member (degradable rubber member) for the downhole tool of the present invention is selected from those formed from a rubber material containing a predetermined amount of decomposing accelerator in the decomposable rubber. Environment [Along with the diversification of depth, etc., most of the temperature is about 60 ° C (140 ° F) to 204 ° C (400 ° F). is there. ], Within a few hours to a few weeks, and optionally within a few days, the degradable seal member for downhole tools loses its sealing function due to the degradation of the degradable rubber promoted by the degradation accelerator. Thus, the seal can be released. About the decomposable protective member for downhole tools, the protection with respect to a sensor, a flow path, etc. is cancelled
- glycolide corresponding to an acid-generating substance
- thermosetting polyurethane urethane rubber having a hardness of A82 °
- Compressive stress reduction rate after immersion for 24 hours (Except for immersion in water at a temperature of 66 ° C., 50% strain compressive stress was measured and calculated in the same manner as “150 ° C. 24-hour compressive stress reduction rate” described above. The same applies to other temperatures.) 32% and mass reduction rate (except for immersion in water at a temperature of 66 ° C.) The same as “150 ° C. 24-hour mass reduction rate” described above.
- thermosetting polyurethane urethane rubber
- MPTS urethane rubber
- the compression stress reduction rate after immersion in water at 66 ° C. for 24 hours is 100. % And mass reduction rate -1.6%, mass reduction rate after 48 hours immersion 3.2%, compression stress reduction rate after 72 hours immersion 100% and mass reduction rate 10.4%, compression after 168 hours immersion Stress reduction rate 100% and mass reduction rate 33.5%, compression stress reduction rate 100% and mass reduction rate 4.5% after immersion in water at 80 ° C.
- thermosetting polyurethane urethane rubber
- a predetermined amount of the following decomposition accelerator is contained.
- Table 1 shows the compressive stress reduction rate and the mass reduction rate.
- the hardness is A96, respectively.
- a thermosetting polyurethane (urethane rubber) having a hardness of 90 ° and a thermosetting polyurethane (urethane rubber) having a hardness of A90 ° were used.
- the downhole tool is provided with other members formed from a decomposable material together with the decomposable rubber member for the downhole tool of the present invention, thereby collecting various members for the downhole tool. The operation of physically destroying can be completely eliminated.
- the downhole tool such as a well drilling plug provided with the decomposable rubber member for the downhole tool of the present invention has various strengths depending on the environment such as various downhole temperatures and the processes performed in the environment.
- the degradable seal member for a downhole tool (degradable rubber member) of the present invention has, for example, temperatures of 177 ° C., 163 ° C., 149 ° C., 121 ° C., 93 ° C., 80
- various downhole temperature environments such as 0 ° C. or 66 ° C., or even 25 to 40 ° C., the seal function can be maintained for a certain period of time, and then the seal function can be lost to release the seal.
- the degree of control and control factors such as the maintenance time of the sealing function and the speed at which the sealing function is lost are determined depending on the type and combination of the decomposition accelerator and degradable rubber. However, it can be adjusted by various methods.
- shape and size of degradable rubber member for downhole tools The shape and size of the degradable rubber member for downhole tools of the present invention are not particularly limited, and the degradable rubber member for downhole tools such as the degradable seal member for downhole tools and the degradable protective member for downhole tools. Can be prepared to suit the type, shape and size of the downhole tool.
- a sheet shape for a downhole tool degradable seal member, a sheet shape (thin film shape, thick plate shape, etc.), rod shape (round bar shape, prismatic shape, etc.), rectangular parallelepiped shape (including cubic shape), ball shape, etc. It may be in the form of a block (fixed shape, irregular shape, etc.).
- the decomposable sealing member for a downhole tool of the present invention is in the form of a sheet, or a sealing material or a packing material (stuffing-like), it is not necessarily a molded body having a predetermined shape.
- the downhole tool including the downhole tool decomposable seal member of the present invention is a well drilling plug or the like
- the downhole tool can be used as a downhole tool decomposable seal member that is an annular molded body. More specifically, it can be a decomposable sealing member for a downhole tool in which an annular molded body is placed on the outer peripheral surface perpendicular to the axial direction of the mandrel provided in the downhole tool, and the like. It can be a decomposable sealing member for a downhole tool provided in a plug for well excavation such as a plug or a bridge plug, and can also be a degradable sealing member for a downhole tool that is a ball or a ball seat.
- a predetermined shape corresponding to the shape of the sheet, sensor, etc. may be of a fixed shape and can be prepared to a size as required. 5.
- Manufacturing method of degradable rubber member for downhole tool The manufacturing method of the degradable rubber member for downhole tool such as the degradable sealing member for downhole tool of the present invention is not particularly limited. For example, by a known molding method such as injection molding, extrusion molding (including solid extrusion molding), centrifugal molding, compression molding, or the like, a predetermined amount of a decomposition accelerator, a decomposable rubber, and other compounding ingredients to be included as required.
- a molded product of a predetermined shape is molded, or a preformed product of a suitable shape (for example, a rod-shaped body or a thick plate) is molded, and then cut as necessary.
- a decomposable rubber member for a downhole tool can be obtained by a combination of methods known per se. II.
- Downhole tool According to the present invention, a downhole tool comprising the above-described decomposable rubber member for a downhole tool is provided.
- the type, shape and size of the downhole tool are not particularly limited.
- the decomposable rubber member for a downhole tool of the present invention includes a seal member in a sleeve system (flux leave), a seal member such as a ball valve and a flapper valve in the downhole tool, and an opening between the downhole tool and the casing.
- a seal member in a sleeve system flux leave
- a seal member such as a ball valve and a flapper valve in the downhole tool and an opening between the downhole tool and the casing.
- sealing members that can temporarily shut off fluids by being placed on the metal
- downhole tool members made of metal, sensors and channels are covered and protected and sealed, and these metal parts are expanded in diameter. By doing so, it can be used as a sealing member in many other sealing applications such as sealing well holes or as a protective member.
- a preferable downhole tool includes a well drilling plug, More preferred are flack plugs and bridge plugs.
- a downhole tool including the decomposable rubber member for downhole tools of the present invention (hereinafter sometimes referred to as “downhole tool of the present invention”), a more preferable plug for well drilling is usually a mandrel (solid). Or may have a hollow portion) and various downhole tool members placed on the outer peripheral surface perpendicular to the axial direction of the mandrel.
- an annular seal member capable of expanding the diameter and sealing the fluid by closing the space between the downhole tool (plug for well excavation) and the casing, and / or Or, a slip, a wedge, a ring, or other member that expands the diameter and fixes the downhole tool (well drilling plug) and the casing to each other, and includes a member known per se (for example, a sensor). Can be.
- the downhaul tool of the present invention includes, for example, a downhole tool degradable seal member (degradable rubber member) which is an annular molded body, and is preferably placed on an outer peripheral surface perpendicular to the axial direction of the mandrel.
- a downhole tool decomposable seal member that is an annular molded body may be provided, and a downhole tool decomposable seal member that is a ball or a ball seat may be provided.
- mandrels such as mandrels, slips, wedges or rings
- materials are conventionally used materials, shapes and sizes, mechanical properties, etc.
- the mandrel it may have a hollow part, may have a diameter that changes along the axial direction, or may have a fixed part, a step part, a concave part, a convex part, etc.
- the decomposable sealing member (decomposable rubber member) for the downhole tool of the present invention is preferably a mandrel provided in the downhole tool, for example, as an annular molded body.
- a mandrel provided in the downhole tool, for example, as an annular molded body.
- annular molded body placed on the outer peripheral surface orthogonal to the axial direction of the member as a member that expands in the direction orthogonal to the axial direction as it is compressed in the axial direction and reduced in diameter, for example, as a ball or a ball sheet
- the space between the borehole casing and the downhole tool can be closed to seal the fluid.
- the degradable rubber member for downhole tools of the present invention is excellent in fluid sealability by being formed from a rubber material containing 0.1 to 20 parts by mass of a decomposition accelerator with respect to 100 parts by mass of degradable rubber. Can be.
- the fluid sealability can be measured by the following method.
- a sample annular rubber member cut into a specific shape with an outer diameter of 90 mm and an inner diameter of 60 mm from a degradable rubber member for downhole tools, an outer cylinder with an inner diameter of 103.1 mm and a core rod with an outer diameter of 60 mm
- the sample is compressed in the axial direction of the jig, and the outer cylinder and core rod part of the jig are the sample (annular rubber member).
- a hydraulic load is applied and seal failure occurs (in many cases, a large deformation force is applied to both ends of the sample, that is, the annular rubber member jig in the axial direction).
- breaking water pressure The water pressure (hereinafter sometimes referred to as “breaking water pressure”) is measured when the part is broken and a sealing failure occurs. If the breaking water pressure is 20 MPa or more, it can be said that the fluid sealability is excellent, preferably 23 MPa or more, more preferably 26 MPa or more.
- the breaking water pressure of the degradable rubber member for downhole tools can be adjusted by the type of degradable rubber, the type and content of the decomposition accelerator, and the like. For example, by adding 5 parts by mass of glycolide as a decomposition accelerator with respect to 100 parts by mass of thermosetting polyurethane (urethane rubber) having a hardness of 90 °, the breaking water pressure can be reduced to about 29 MPa.
- the breaking water pressure exceeds 46 MPa (even if a water pressure of 46 MPa is loaded, Seal failure does not occur.). Furthermore, by adding 0.1 part by mass of MPTS as a decomposition accelerator to 100 parts by mass of thermosetting polyurethane (urethane rubber) having a hardness of 90 °, the fracture hydraulic pressure can be reduced to about 37 MPa. By containing 0.5 part by mass of the material, the breaking water pressure can be set to about 30 MPa. III.
- the well drilling method using the degradable rubber member for downhole tools of the present invention for example, using a downhole tool such as a well drilling plug provided with a degradable seal member for downhole tools
- a downhole tool such as a well drilling plug provided with a degradable seal member for downhole tools
- the decomposable rubber member for downhole tools of the present invention for example, a well equipped with a degradable seal member for downhole tools.
- the fracturing of the predetermined sections is completed.
- the seal with the degradable seal member for the downhole tool that closes the well hole It can be designed so that the seal can be easily released within a desired period in a downhole environment.
- the protection for the sensor, the flow path, etc. can be canceled within a desired period in the downhole environment.
- the diameter expands in the direction perpendicular to the axial direction of the mandrel, and the outer part in the direction perpendicular to the axial direction is the inner wall of the downhole And the inner part in the direction orthogonal to the axial direction abuts on the outer peripheral surface of the mandrel, thereby closing the space between the downhole tool and the downhole and sealing the fluid.
- a downhole tool such as a well drilling plug according to the present invention is generally used after completion of fracturing of predetermined sections, and the drilling of the well is completed and the well is completed, such as oil and natural gas.
- the seal function of the degradable seal member is lost, and if desired, it can be easily disassembled or collapsed with other downhole tool members other than the degradable seal members for downhole tools such as mandrels, slips, rings, etc. Can be removed. That is, after performing the sealing process of the well hole using the decomposable sealing member for downhole tool of the present invention, the degradable sealing member for downhole tool loses the sealing function and is further disassembled as desired. (I) The seal for preventing fluid movement in the well can be released within a desired period.
- the degradable rubber member for downhole tools remaining after the completion of the well treatment has completely disappeared before the start of production, but the strength is reduced even if it has not completely disappeared. If it becomes a state that collapses due to a stimulus such as a water flow in the downhole, the disintegratable rubber member for the downhole tool can be easily recovered by a flowback, etc. Since clogging does not occur, there is no obstacle to production of oil or natural gas.
- the decomposable rubber member for downhole tool is decomposed and the strength is lowered in a shorter time.
- the water content in the formation may be low. In this case, the water-based fluid used during fracturing is left in the well without being recovered after fracturing. Can be promoted.
- the downhole is formed in the wellbore.
- a well drilling method characterized in that a degradable rubber member for hall tools is decomposed, ii) a degradable rubber member for downhole tools according to the present invention, and further containing a degradable material (preferably PGA)
- a degradable material preferably PGA
- a degradable rubber member for a downhole tool of the present invention wherein the degradable rubber member for a downhole tool is in contact with another downhole tool member, and / or The downhole tool decomposable rubber member is decomposed in the well hole after the well treatment is performed using the downhole tool arranged to cover the other downhole tool member.
- a well excavation method is provided.
- the present invention is a degradable rubber member for downhole tools, characterized in that it is formed from a rubber material containing 0.1 to 20 parts by mass of a decomposition accelerator with respect to 100 parts by mass of degradable rubber. Designed as desired so that fluids can be reliably sealed to facilitate well treatment, and the seal can be removed and removed and secured in the desired period as the mining conditions vary. It can be applied to degradable sealing members that can be designed and designed to be able to be easily removed after protecting the sensors, flow paths, etc.
- a decomposable rubber member for a hall tool can be provided, and further, a downhole tool including the member and a well excavation method can be provided. Therefore, industrial applicability is high.
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Abstract
Description
(2)分解性ゴム100質量部に対して分解促進剤0.1~20質量部を含有するゴム材料から形成され、温度150℃の水に24時間浸漬後の質量または50%ひずみ圧縮応力の、浸漬前の質量または50%ひずみ圧縮応力に対する減少率が5%以上であることを特徴とするダウンホールツール用分解性ゴム部材。
(3)温度150℃の水に72時間浸漬後の質量の、浸漬前の質量に対する減少率が5~100%である前記(2)のダウンホールツール用分解性ゴム部材。
(4)分解性ゴム100質量部に対して分解促進剤0.1~20質量部を含有するゴム材料から形成され、温度150℃の水に72時間浸漬後の質量の、浸漬前の質量に対する減少率が5~100%であることを特徴とするダウンホールツール用分解性ゴム部材。
(5)温度66℃における引張破断ひずみが50%以上、70%ひずみ圧縮応力が10MPa以上かつ圧縮破断ひずみが50%以上である前記(1)~(4)のいずれかのダウンホールツール用分解性ゴム部材。
(6)表面硬度がA60~D80の範囲内である前記(5)のダウンホールツール用分解性ゴム部材。
(7)温度66℃において、圧縮ひずみ5%における圧縮応力に対する、圧縮ひずみ70%における圧縮応力の比率が5倍以上である前記(1)~(6)のいずれかのダウンホールツール用分解性ゴム部材。
(8)ドライ環境下で安定であり、温度23℃の水に6時間浸漬後の50%ひずみ圧縮応力の、1時間浸漬後の50%ひずみ圧縮応力に対する減少率が5%未満である前記(1)~(7)のいずれかのダウンホールツール用分解性ゴム部材。
(9)分解促進剤が酸性物質である前記(1)~(8)のいずれかのダウンホールツール用分解性ゴム部材。
(10)酸性物質が酸生成物質である前記(9)のダウンホールツール用分解性ゴム部材。
(11)分解促進剤が可塑剤である前記(1)~(8)のいずれかのダウンホールツール用分解性ゴム部材。
(12)分解促進剤が、有機酸、無機酸、有機酸エステル、無機酸エステル及び酸無水物からなる群より選ばれる少なくとも1種を含有する前記(1)~(8)のいずれかのダウンホールツール用分解性ゴム部材。
(13)分解促進剤が、グリコリド、ラクチド、ε-カプロラクトン、ポリグリコール酸、ポリ乳酸、p-トルエンスルホン酸メチル及び3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物からなる群より選ばれる少なくとも1種を含有する前記(1)~(8)のいずれかのダウンホールツール用分解性ゴム部材。
(14)分解性ゴムは、ウレタンゴム、天然ゴム、イソプレンゴム、エチレンプロピレンゴム、ブチルゴム、スチレンゴム、アクリルゴム、脂肪族ポリエステルゴム、クロロプレンゴム、ポリエステル系熱可塑性エラストマー及びポリアミド系熱可塑性エラストマーからなる群より選ばれる少なくとも1種を含有する前記(1)~(13)のいずれかのダウンホールツール用分解性ゴム部材。
(15)分解性ゴムは、加水分解性の官能基を有するゴムを含有する前記(1)~(14)のいずれかのダウンホールツール用分解性ゴム部材。
(16)ゴム材料は、強化材を含有する前記(1)~(15)のいずれかのダウンホールツール用分解性ゴム部材。
(17)温度23℃における曲げ弾性率が0.005~10GPaの範囲である前記(1)~(16)のいずれかのダウンホールツール用分解性ゴム部材。
(18)シール部材である前記(1)~(17)のいずれかのダウンホールツール用分解性ゴム部材。
(19)環状の成形体である前記(18)のダウンホールツール用分解性ゴム部材。
(20)環状の成形体が、ダウンホールツールに備えられるマンドレルの軸方向と直交する外周面上に置かれるものである前記(19)のダウンホールツール用分解性ゴム部材。
(21)ボールまたはボールシートである前記(1)~(17)のいずれかのダウンホールツール用分解性ゴム部材。
(22)ダウンホールツール用分解性保護部材である前記(1)~(17)のいずれかのダウンホールツール用分解性ゴム部材。
(23)坑井掘削用プラグに備えられる前記(1)~(22)のいずれかのダウンホールツール用分解性ゴム部材。
(29)前記(1)~(23)のいずれかのダウンホールツール用分解性ゴム部材を備えるダウンホールツールを使用して、坑井孔をシールした後に、坑井孔内で該ダウンホールツール用分解性ゴム部材が分解されることを特徴とする坑井掘削方法。
(30)前記(1)~(23)のいずれかのダウンホールツール用分解性ゴム部材を備え、さらに分解性材料を含有する他のダウンホールツール用部材を備えるダウンホールツールを使用して、坑井孔をシールした後に、坑井孔内で該ダウンホールツール用分解性ゴム部材が分解されることを特徴とする坑井掘削方法。
(31)他のダウンホールツール用部材に含有される分解性材料がポリグリコール酸である前記(30)の坑井掘削方法。
(32)前記(1)~(23)のいずれかのダウンホールツール用分解性ゴム部材を備え、該ダウンホールツール用分解性ゴム部材が、他のダウンホールツール用部材に接する、及び/または、他のダウンホールツール用部材を覆うように配置されてなるダウンホールツールを使用して、坑井処理を行った後に、坑井孔内で該ダウンホールツール用分解性ゴム部材が分解されることを特徴とする坑井掘削方法。
本発明の第1の側面によるダウンホールツール用分解性ゴム部材は、分解性ゴムに所定量の分解促進剤を含有するゴム材料から形成されることを特徴とする。そして、本発明のダウンホールツール用分解性ゴム部材は、ダウンホールツール用分解性シール部材やダウンホールツール用分解性保護部材に適用されることによって、坑井掘削の経費軽減や工程短縮ができる効果を奏するものである。以下、主としてダウンホールツール用分解性シール部材の具体例を示しながら、本発明のダウンホールツール用分解性ゴム部材を説明する。
1.分解性ゴム
分解促進剤を所定量含有して、本発明のダウンホールツール用分解性シール部材(分解性ゴム部材)を形成するゴム材料となる分解性ゴムとしては、従来、ダウンホールツール用分解性シール部材を形成するために使用されていた分解性ゴムを使用することができる。ダウンホールツール用分解性シール部材を形成するゴム材料に含有される分解性ゴムは、1種単体で使用してもよいが、2種以上の分解性ゴムを混合して使用してもよい。
〔分解性〕
ダウンホールツール用分解性ゴム部材(分解性シール部材)を形成するゴム材料に含有される分解性ゴムにおける分解性とは、例えば、フラクチャリング等の坑井処理が実施される土壌中の微生物によって分解される生分解性、または、フラクチャリング流体等の溶媒、特に、水によって、更に所望により酸またはアルカリによって分解する加水分解性、中でも所定温度以上の水によって分解する加水分解性、更に他の何らかの方法によって化学的に分解することができる分解性を意味するほか、例えば、重合度の低下等によりゴムが本来有した強度が低下して脆くなる結果、極めて小さい機械的力を加えることにより、ダウンホールツール用のシール部材(分解性ゴム部材)が簡単に崩壊して形状を失うこと(崩壊性)も意味する。
〔分解性ゴムの具体例〕
本発明のダウンホールツール用分解性シール部材(分解性ゴム部材)を形成するゴム材料に含有される分解性ゴムは、ウレタンゴム、天然ゴム、イソプレンゴム、エチレンプロピレンゴム、ブチルゴム、スチレンゴム、アクリルゴム、脂肪族ポリエステルゴム、クロロプレンゴム、ポリエステル系熱可塑性エラストマー及びポリアミド系熱可塑性エラストマーからなる群より選ばれる少なくとも1種を含有する分解性ゴムが挙げられる。さらに、例えば後述する150℃24時間圧縮応力減少率が5%未満であるような必ずしも分解性ゴムとはいえないゴム、いわば非分解性ゴムであっても、後に説明する分解促進剤を所定量含有するゴム材料とすることによって、ダウンホールツール用分解性シール部材を形成することができることがあり、この場合は、当該いわば非分解性ゴムも、本発明の分解性ゴムに該当する。
〔ウレタンゴム〕
本発明のダウンホールツール用分解性シール部材(分解性ゴム部材)を形成するゴム材料に含有される分解性ゴムとして特に好ましく使用されるウレタンゴム(「ウレタンエラストマー」ということもある。)は、分子中にウレタン結合(-NH-CO-O-)を有するゴム材料であり、通常、イソシアネート化合物と水酸基を有する化合物とを縮合して得られる。イソシアネート化合物としては、芳香族(複数の芳香族環を有してもよい。)、脂肪族、脂環族系のジ、トリ、テトラ系のポリイソシアネート類、またはこれらの混合物が用いられる。水酸基を有する化合物として、その主鎖にエステル結合を有するポリエステル型ウレタンゴム(以下、「エステル型ウレタンゴム」ということがある。)とその主鎖にエーテル結合を有するポリエーテル型ウレタンゴム(以下、「エーテル型ウレタンゴム」ということがある。)とに大別され、分解性や崩壊性の制御がより容易であることから、エステル型ウレタンゴムが好ましい場合が多い。ウレタンゴムは合成ゴムの弾性(柔らかさ)とプラスチックの剛性(固さ)を併せ持った弾性体であり、一般に、耐摩耗性、耐薬品、耐油性に優れ、機械的強度が大きく、耐荷重性が大きく、高弾性でエネルギー吸収性が高いことが知られている。ウレタンゴムとしては、成形方法の差異によって、i)混練(ミラブル)タイプ:一般のゴムと同じ加工方法で成形できる、ii)熱可塑性タイプ:熱可塑性樹脂と同じ加工方法で成形できる、及びiii)注型タイプ:液状の原料を使用して熱硬化する加工方法で成形できる、というタイプ区分がされるが、本発明のダウンホールツール用分解性シール部材を形成するウレタンゴムとしては、いずれのタイプのものも使用することができる。
〔ポリエステル系熱可塑性エラストマー〕
本発明のダウンホールツール用分解性シール部材(分解性ゴム部材)を形成するゴム材料に含有される分解性ゴムとして好ましく使用されるポリエステル系熱可塑性エラストマーは、ポリエステル系ブロック共重合体を主成分としたエラストマーである。具体的には、例えばポリエステルからなるハードセグメントとポリエーテルからなるソフトセグメントとのブロック共重合体があり、ハードセグメントとして、芳香族ポリエステルや脂肪族ポリエステル、より具体的にはポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ポリヒドロキシアルカン酸等が挙げられ、ソフトセグメントとして、例えばポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレンエーテルグリコール等のポリエーテルが挙げられる。またハードセグメント及びソフトセグメントがポリエステルからなるブロック共重合体があり、ハードセグメントとして、芳香族ポリエステル、より具体的にはポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート等が挙げられ、ソフトセグメントとしては、ハードセグメントより低弾性率の脂肪族ポリエステル、例えばアルキル鎖長が2以上のポリヒドロキシアルカン酸が挙げられる。これらのハードセグメント及びソフトセグメントは、所望のエラストマーの物性、特に所望の分解特性及び機械特性に適合するように、ハードセグメントとソフトセグメントの種類またはこれらの比率を調整することが可能であり、更に必要に応じて各種配合剤との組み合わせによって所望の物性を有するポリエステル系熱可塑性エラストマーを得ることができる。ポリエステル系熱可塑性エラストマーは、プラスチックとゴムの両特性を備えており、射出成形、押出成形、ブロー成形等の各種成形加工が可能であり、また、エステル結合を有していることにより、所定時間で分解や崩壊しやすい特性がある。
〔ポリアミド系熱可塑性エラストマー〕
本発明のダウンホールツール用分解性シール部材(分解性ゴム部材)を形成するゴム材料に含有される分解性ゴムとして好ましく使用されるポリアミド系熱可塑性エラストマーは、ポリアミドからなるハードセグメントとポリエーテル及び/またはポリエステルからなるソフトセグメントとのブロック共重合体である。具体的には、ハードセグメントとしては、例えば、脂肪族ポリアミド、より具体的にはナイロン6、ナイロン11、ナイロン12が挙げられ、ソフトセグメントとしては、例えばポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレンエーテルグリコール等のポリエーテルが挙げられる。これらのハードセグメント及びソフトセグメントは、所望のエラストマーの物性、特に所望の分解特性及び機械特性に適合するように、ハードセグメントとソフトセグメントの種類またはこれらの比率を調整することが可能であり、更に必要に応じて各種配合剤との組み合わせによって所望の物性を有するポリアミド系熱可塑性エラストマーを得ることができる。ポリアミド系熱可塑性エラストマーは、ゴムとプラスチックの中間的な性質を有し、射出成形、押出成形、ブロー成形等の各種成形加工が可能であり、また、アミド結合を有していることにより、高温高圧下で加水分解を生じ、易分解や易崩壊となる特性がある。
2.分解促進剤
本発明のダウンホールツール用分解性シール部材(分解性ゴム部材)に含有される分解促進剤とは、ダウンホールツール用分解性シール部材が使用されるダウンホール環境下において、分解性ゴムの分解や崩壊を促進することができる配合剤であり、特に、分解性ゴムの分解、中でも加水分解を促進することができるゴム材料に含有される配合剤である。分解性ゴムの分解を確実に果たす効果が期待できることから、分解促進剤としては、分解性ゴムのゴム分子の主鎖の結合を切断する機能または分解性ゴムを可塑化する機能を有する配合剤であることが好ましく、したがって、分解促進剤として好ましくは、酸性物質及び可塑剤が挙げられる。また、分解促進剤が、有機酸、無機酸、有機酸エステル、無機酸エステル及び酸無水物からなる群より選ばれる少なくとも1種を含有するものであることが好ましい。
〔酸性物質〕
本発明のダウンホールツール用分解性シール部材(分解性ゴム部材)において、好ましい分解促進剤として酸性物質が挙げられる。酸性物質は、ダウンホールツール用分解性シール部材(分解性ゴム部材)を形成するゴム部材に含有される分解性ゴムのゴム分子の主鎖の結合を切断することによって、該ゴム部材の分解を促進し、その結果、ダウンホールツール用分解性シール部材の分解が促進される。すなわち、ダウンホールツール用分解性シール部材が、酸性物質を含有する分解性ゴムであるゴム材料から形成される場合、分解性ゴムの内部に、通常は均質に分散して、酸性物質が存在することにより、酸性物質が分解性ゴムの分子の多くに接触することができるので、例えば、ゴム材料から形成されるダウンホールツール用分解性シール部材を水(酸性物質を含有してもよい。)に浸漬する場合のように、該シール部材の表面から分解が進行する場合と比較して、より大きな速度で分解性ゴムの分解が進行するものと推察される。
〔可塑剤〕
また、本発明のダウンホールツール用分解性シール部材(分解性ゴム部材)において、好ましい分解促進剤として可塑剤が挙げられる。可塑剤は、ダウンホールツール用分解性シール部材(分解性ゴム部材)を形成するゴム部材に含有される分解性ゴムを可塑化する機能(トルク低下、軟化等)を有するものである結果、分解性ゴムを分解、例えば加水分解する水(酸性物質またはアルカリ性物質を含有してもよい。)のダウンホールツール用分解性シール部材(分解性ゴム部材)への浸入が促進されるので、先に酸性物質について説明したと同様に、ダウンホールツール用分解性シール部材(分解性ゴム部材)の表面から分解が進行する場合と比較して、より大きな速度で分解性ゴムの分解が進行するものと推察される。可塑剤としては、例えば、ジブチルフタレート、ジイソノニルフタレート、ジオクチルフタレート、ジオクチルアジペート、ジイソノニルアジペート、ジブチルセバケート等を挙げることができるが、分解性ゴムに対する可塑化効果の有無や大小が異なるので、好適な可塑剤の種類は、分解性ゴムとの組み合わせによって定まる。分解性ゴム100質量部に対する可塑剤の含有量は、特に限定されず、先に説明した可塑剤と分解性ゴムとの組み合わせによって分解促進効果を発揮する最適範囲を定めることができるが、通常0.1~20質量部であり、多くの場合0.3~15質量部、ほとんどの場合0.5~10質量部の範囲で分解性ゴムに対する分解促進効果を有する。
〔分解促進剤の使用〕
分解促進剤としては、好ましく挙げた酸性物質及び可塑剤のほか、分解性ゴムの分解、特に加水分解を促進する効果を奏するものを使用することができる。分解促進剤は、1種の化合物単独でもよいし、2種以上の化合物を含有してもよく、また、例えば酸性物質と可塑剤とを含有してもよい。また、先に酸性物質について説明したように、分解促進剤の含有態様としては、相溶性でもよいし、顆粒状でもよいが、ゴム材料からダウンホールツール用分解性シール部材(分解性ゴム部材)を形成するまでの間(分解性ゴムの重合中、溶融混練または溶融成形中など)に、分解したり揮散したりして消失しないことが必要である。分解促進剤の含有量は、分解促進剤と分解性ゴムとの組み合わせによって最適範囲を選択することができるが、分解性ゴム100質量部に対して通常0.1~20質量部であり、多くの場合0.3~15質量部、ほとんどの場合0.5~10質量部の範囲で分解性ゴムに対する分解促進効果を有する。分解促進剤の含有量が少なすぎると、分解性ゴムに対する分解促進効果が不足し、所望の期間内にダウンホールツール用分解性シール部材を分解してシールを解除できなくなるおそれがあり、坑井掘削の経費軽減や工程短縮が損なわれることがある。分解促進剤の含有量が多すぎると、フラクチャリング等の坑井処理において、ダウンホールツール用分解性シール部材による流体シールが必要とされる期間が経過する前に、シールが解除されてしまうおそれがあり、坑井掘削に大きな支障を生じることがある。したがって、分解促進剤の種類または分解促進剤の含有量により分解速度を制御することが可能である。本発明のダウンホールツール用分解性シール部材は、分解性ゴム100質量部に対して分解促進剤0.1~20質量部を含有するゴム材料から形成されることにより、分解性ゴムの分解が促進されるので、坑井処理の終了後に行う、または坑井掘削の完了後に行う、ダウンホールツール用分解性シール部材によるシールの解除を、より低温で、及び/またはより短時間で実施することができるので、採掘条件が多様となるもと、所望の期間でシールの解除を行うことができ、坑井掘削の経費軽減や工程短縮ができる。さらに、ダウンホールツール用分解性シール部材を形成するゴム材料に含有される分解性ゴムを、該シール部材の表面からでなく内部から分解することができるので、シール解除後のダウンホールツール用分解性シール部材を、従来より微粉化することができるので、坑井処理終了後や坑井掘削完了後の回収操作が容易かつ迅速に行えるようになる。
3.分解性ゴム100質量部に対して分解促進剤0.1~20質量部を含有するゴム材料
〔他の配合成分〕
本発明のダウンホールツール用分解性シール部材(分解性ゴム部材)は、分解性ゴム100質量部に対して分解促進剤0.1~20質量部を含有するゴム材料から形成されることを特徴とするが、ダウンホールツール用分解性シール部材(分解性ゴム部材)を形成するゴム材料は、分解性ゴム及び所定量の分解促進剤に加えて、本発明の目的を阻害しない範囲で、更に他の配合成分として、他の樹脂(分解性ゴム以外の分解性高分子や、分解性を有しない樹脂やゴムでもよい。)や、安定剤、着色剤、強化材等の各種添加剤を含有することができる。特に、ダウンホールツール用分解性シール部材(分解性ゴム部材)を形成するゴム材料は、強化材を含有してもよい。なお、分解性ゴム100質量部に対して分解促進剤0.1~20質量部を含有するゴム材料が、分解性ゴム以外の分解性高分子や、分解性を有しない樹脂やゴムを含有する場合、該ゴム材料に含有される分解促進剤は、分解性ゴム100質量部に対して0.1~20質量部である割合で含有されるように調製される。
〔強化材〕
強化材としては、従来、機械的強度や耐熱性の向上を目的として樹脂材料等の強化材として使用されている材料を使用することができ、繊維状強化材や、粒状または粉末状強化材を使用することができる。強化材は、分解性ゴム100質量部に対して、通常150質量部以下、好ましくは10~100質量部の範囲で含有させることができる。本発明のダウンホールツール用分解性シール部材(分解性ゴム部材)を形成するゴム材料が、強化材を含有するものであると、ダウンホール環境が分解性ゴムの融点(溶融軟化点)に近い環境であっても、処理に必要な期間、シール(分解性ゴム部材においては保護)を行うことが可能となることがある。
〔他の樹脂〕
本発明の目的を阻害しない範囲で、更に他の配合成分として含有することができる他の樹脂(分解性ゴム以外の分解性高分子や、分解性を有しない樹脂やゴムでもよい。)としては、シール機能の喪失を促進することが所望される場合には、分解性ゴム以外の分解性高分子である、例えば、ポリグリコール酸、ステレオコンプレックス型ポリ乳酸、ポリブチレンサクシネート、ポリブチレンアジペート/テレフタレート、及びポリブチレンサクシネート/アジペートなどを含有することができる。
4.ダウンホールツール用分解性ゴム部材
分解性ゴム100質量部に対して分解促進剤0.1~20質量部を含有するゴム材料から形成される本発明のダウンホールツール用分解性シール部材等のダウンホールツール用分解性ゴム部材は、従来、使用されていたダウンホールツール用分解性シール部材やダウンホールツール用分解性保護部材と同様の構成、構造、形状を有するものとすることができ、また、従来と同様の機械的特性等を有するものとすることができ、これによって、従来と同様の用途や使用態様に適用することができる。以下、ダウンホールツール用分解性シール部材の具体例について説明する。
〔150℃24時間質量減少率〕
本発明のダウンホールツール用分解性ゴム部材は、さらに、ダウンホール環境において、確実に分解性を発揮する観点から、温度150℃の水に24時間浸漬後の質量の、浸漬前の質量に対する減少率(以下、「150℃24時間質量減少率」ということがある。)が5%以上であることが好ましい。ダウンホールツール用分解性ゴム部材の150℃24時間質量減少率は、厚み、長さ及び幅各20mmに切り出したダウンホールツール用分解性ゴム部材の試料を、温度150℃の水(脱イオン水等)400mL中に浸漬し、24時間経過後に取り出した後に測定した試料の質量と、予め温度150℃の水に浸漬する前に測定した試料の質量(以下、「当初質量」ということがある。)とを比較して、当初質量に対する減少率(単位:%)を算出するものである。なお、温度150℃の水に浸漬中に、ダウンホールツール用分解性ゴム部材が、分解したり溶出したりして形状を失いまたは消失する場合は、前記の質量減少率を100%とする。
〔150℃24時間圧縮応力減少率〕
本発明のダウンホールツール用分解性ゴム部材は、ダウンホール環境において、確実に分解性を発揮する観点から、温度150℃の水に24時間浸漬後の50%ひずみ圧縮応力の、浸漬前の50%ひずみ圧縮応力に対する減少率(以下、「150℃24時間圧縮応力減少率」ということがある。)が5%以上であることが好ましい。ダウンホールツール用分解性ゴム部材の150℃24時間圧縮応力減少率の測定方法は以下のとおりである。すなわち、所定形状の試料(厚み、長さ及び幅各5mmに切り出した試料を使用する。)を、温度150℃の水(脱イオン水等)400mL中に浸漬し、24時間経過後に取り出して、JIS K7181(ISO604準拠)に従って、常温で圧縮応力を測定し、圧縮ひずみ50%における圧縮応力(単位:MPa。以下「50%ひずみ圧縮応力」ということがある。)を求める。予め温度150℃の水に浸漬する前に測定した50%ひずみ圧縮応力(「当初の圧縮応力」)の値と比較して、当初の圧縮応力に対する減少率(単位:%)を算出する。なお、温度150℃の水に浸漬中に、ダウンホールツール用分解性ゴム部材が、分解したり溶出したりして形状を失ったり消失したりする場合、または、圧縮応力を測定しているときに50%ひずみ到達前にダウンホールツール用分解性ゴム部材が崩壊する場合は、前記の減少率を100%とする。
〔150℃72時間質量減少率〕
本発明のダウンホールツール用分解性ゴム部材は、さらに、ダウンホール環境において、確実に分解性を発揮する観点から、温度150℃の水に72時間浸漬後の質量の、浸漬前の質量に対する減少率(以下、「150℃72時間質量減少率」ということがある。)が5~100%であることが好ましい。ダウンホールツール用分解性ゴム部材の150℃72時間質量減少率は、先に150℃24時間質量減少率について説明したと同様にして、厚み、長さ及び幅各20mmに切り出したダウンホールツール用分解性ゴム部材の試料を、温度150℃の水(脱イオン水等)400mL中に浸漬し、72時間経過後に取り出した後に測定した試料の質量と、予め温度150℃の水に浸漬する前に測定した試料の質量(当初質量)とを比較して、算出するものである。ダウンホールツール用分解性ゴム部材が、150℃72時間質量減少率が5~100%であることにより、ダウンホール環境(深度の多様化等に付随し約60℃程度~200℃程度の温度であり、近年は更に25~40℃程度の低温のダウンホール環境もある。)において、数時間~数週間以内で、所定量の分解促進剤を含有するゴム材料から形成されるダウンホールツール用分解性ゴム部材(分解性シール部材)が分解または崩壊、更に望ましくは消失(本発明においては、総称して「分解」ということがある。)することにより、ダウンホールツール用分解性ゴム部材(分解性シール部材)によるシール機能が喪失されるので坑井掘削のための経費軽減や工程短縮に寄与することができる。ダウンホールツール用分解性ゴム部材(分解性シール部材)には、種々のダウンホールの温度等の環境や当該環境において実施する工程に応じて、多様なシール機能の機能維持時間及び機能喪失時間が求められるが、本発明のダウンホールツール用分解性ゴム部材(分解性シール部材)は、150℃72時間質量減少率が、より好ましくは10~100%、更に好ましくは50~100%、特に好ましくは80~100%、最も好ましくは90~100%であることにより、後に説明する分解促進剤の機能と相まって、例えば、温度177℃、163℃、149℃、121℃、93℃、80℃または66℃、更には25~40℃などの種々のダウンホールの温度環境において、一定時間シール機能を発揮し、その後シール機能を喪失してシールを解除する特性を有するものとすることができる。ダウンホールツール用分解性ゴム部材の150℃72時間質量減少率を制御する因子や制御できる程度は、先に150℃24時間質量減少率について説明したと同様である。
〔66℃引張破断ひずみ〕
本発明のダウンホールツール用分解性ゴム部材は、所望により、温度66℃における引張破断ひずみ(以下、「66℃引張破断ひずみ」ということがある。)が50%以上であることにより、フラクチャリング等の坑井処理を行うのに要する期間、ダウンホールツール用分解性ゴム部材の強度が維持され、ダウンホールの閉塞(分解性保護部材についてはセンサー等の保護。以下同様である。)をより確実に継続できるので好ましい。すなわち、ダウンホールツール用分解性ゴム部材を使用して坑井孔の閉塞(シール)を行う場合に、ダウンホールツール用分解性ゴム部材が、ダウンホールツールの形状及びダウンホールの形状(ケーシングの形状)に確実に係合するように変形しても、具体的には大きな引張力(及び圧縮力)を受けながら変形しても、破断するおそれがないので、ダウンホールツール用分解性ゴム部材とケーシングとの当接面積が大きくなり、閉塞が確実となる。さらに、例えばフラクチャリング等のシールが必要とされる処理を実施するために、流体による極めて高い圧力が負荷されることで、大きな引張力(及び圧縮力)を受けることがあっても、流体のシールが破壊されにくい効果がある。66℃引張破断ひずみは、ISO37(JIS K6251)に準拠して、温度66℃で測定するものである。66℃引張破断ひずみは、より好ましくは80%以上、更に好ましくは100%以上である。66℃引張破断ひずみは、上限値が特にないが、66℃引張破断ひずみが大きすぎると、所要の坑井処理後にダウンホールツール用分解性ゴム部材を分解させて強度が失われる際に小片となりにくくなる場合があることから、通常500%以下、多くの場合480%以下である。
〔66℃圧縮応力〕
本発明のダウンホールツール用分解性ゴム部材は、所望により、温度66℃における70%ひずみ圧縮応力(以下、「66℃圧縮応力」ということがある。)が10MPa以上であることにより、フラクチャリング等の坑井処理を行うのに要する期間、ダウンホールツール用分解性ゴム部材の強度が維持され、ダウンホールの閉塞をより確実に継続できるので好ましい。すなわち、ダウンホールツール用分解性ゴム部材を使用して坑井孔の閉塞(シール)を行う場合に、ダウンホールツール用分解性ゴム部材が、ダウンホールツールの形状及びダウンホールの形状(ケーシングの形状)に確実に係合するように変形しても、具体的には大きな圧縮力(及び引張)を受けながら変形しても、破断するおそれがないので、ダウンホールツール用分解性ゴム部材とケーシングとの当接面積が大きくなり、閉塞が確実となる。さらに、例えばフラクチャリング等のシールが必要とされる処理を実施するために、流体による極めて高い圧力が負荷されることで、大きな圧縮力(及び引張力)を受けることがあっても、流体のシールが破壊されにくい効果がある。66℃圧縮応力は、ISO14126(JIS K7018)に準拠して、温度66℃で測定する、圧縮ひずみ70%における圧縮応力(単位:MPa)または圧縮ひずみ70%到達以前に破断する際には破断時までの最大応力値を表す。66℃圧縮応力は、より好ましくは20MPa以上、更に好ましくは30MPa以上である。66℃圧縮応力は、上限値が特にないが、通常200MPa以下、多くの場合150MPa以下である。
〔66℃圧縮破断ひずみ〕
本発明のダウンホールツール用分解性ゴム部材は、所望により、温度66℃における圧縮破断ひずみ(以下、「66℃圧縮破断ひずみ」ということがある。)が50%以上であることにより、フラクチャリング等の坑井処理を行うのに要する期間、ダウンホールツール用分解性ゴム部材の強度が維持され、ダウンホールの閉塞をより確実に継続できるので好ましい。66℃圧縮破断ひずみは、ISO14126に準拠して、温度66℃で測定するものである。66℃圧縮破断ひずみは、より好ましくは60%以上、更に好ましくは70%以上である。66℃圧縮破断ひずみは、上限値が100%であるが、通常99%以下である。
〔表面硬度〕
本発明のダウンホールツール用分解性ゴム部材は、先に説明した66℃引張破断ひずみ、66℃圧縮応力及び66℃圧縮破断ひずみの所望の特性に加えて更に、シール機能の観点から表面硬度がA60~D80の範囲であることが好ましい。ダウンホールツール用分解性ゴム部材を形成するゴム材料の表面硬度とは、ISO7619に準拠して測定されるデュロメータ硬度のタイプA(以下、「表面硬度A」または単に「硬度A」ということがある。)またはタイプD(以下、「表面硬度D」または単に「硬度D」ということがある。)で表される表面硬度を意味するものである。デュロメータ硬度としては、一般ゴム等に適合する中硬さ用のタイプA、硬質ゴム等に適合する高硬さ用のタイプD、及びスポンジ等に適合する低硬さ用のタイプEがある(例えば、硬度A100は、概ね硬度D60程度に相当することが多い。)。本発明のダウンホールツール用分解性ゴム部材を形成するゴム材料は、硬度A60~D80の範囲であることによって、更に所望によりゴム部材の構造等を併せて調整することにより、フラクチャリング等の高圧流体加圧に抗して坑井孔のシールを行うことができるよう構成することができる。ダウンホールツール用分解性ゴム部材を形成するゴム材料の表面硬度は、より好ましくは表面硬度A65~D78、更に好ましくは表面硬度A70~D75の範囲である。
〔23℃圧縮応力減少率〕
本発明のダウンホールツール用分解性ゴム部材は、更に所望により、ドライ環境下で安定であり、温度23℃の水に6時間浸漬後の50%ひずみ圧縮応力の、1時間浸漬後の50%ひずみ圧縮応力に対する減少率(以下、「23℃圧縮応力減少率」ということがある。)が5%未満であることにより、フラクチャリング等の坑井処理を行うのに要する期間、ダウンホールツール用分解性ゴム部材の強度が維持され、ダウンホールの閉塞をより確実に継続できるので好ましい。すなわち、坑井掘削のための採掘条件が多様なものとなっているもとで、予期しない短時間で、ダウンホールの閉塞(保護部材において、センサー等の保護機能)が喪失されるようなことがない。特に、ダウンホールツール用分解性ゴム部材は、ドライ環境下で安定であることにより、本発明のダウンホールツール用分解性ゴム部材を備えるダウンホールツールを坑井孔内に配置し、フラクチャリング等の坑井処理を行うに至る前段階において、シール機能(保護部材においては、保護機能)を喪失することがない。ダウンホールツール用分解性ゴム部材の23℃圧縮応力減少率の測定方法は、先に説明した150℃24時間圧縮応力減少率の測定方法と同様であり、温度150℃の水に浸漬するのに代えて、温度23℃の水に、所要時間浸漬することにより測定することができる。23℃圧縮応力減少率は、より好ましくは4%未満、更に好ましくは3%未満である。23℃圧縮応力減少率は、下限値が0%である。なお、本発明のダウンホールツール用分解性ゴム部材について、「ドライ環境下で安定」であるとは、温度23℃相対湿度50%の環境下において168時間(7日間)以上、圧縮応力の減少が生じないことをいう。
〔66℃圧縮応力比率〕
本発明のダウンホールツール用分解性ゴム部材は、更に所望により、温度66℃において、圧縮ひずみ5%における圧縮応力に対する、圧縮ひずみ70%における圧縮応力の比率(以下、「66℃圧縮応力比率」ということがある。)が5倍以上であることにより、フラクチャリング等の坑井処理を行うのに要する期間、ダウンホールツール用分解性ゴム部材の強度が維持され、ダウンホールの閉塞をより確実に継続できるので好ましい。すなわち、ダウンホールツール用分解性ゴム部材を使用して坑井孔の閉塞(シール)を行う場合に、ダウンホールツール用分解性ゴム部材の初期の圧縮ひずみが小さい(変形しやすい)ため、ダウンホールツールの形状及びダウンホールの形状(ケーシングの形状)に確実に係合するように変形可能であって、さらに、大きな圧縮力(及び引張力)を受けながら変形する際には、変形量が大きな領域でゴム部材の応力が大きく立ち上がることで、例えばゴム部材とケーシングの当接部分のゴム部材が高い圧縮応力(及び引張力)を有する状態となるので、例えばフラクチャリング等のシールが必要とされる坑井処理を実施する際に、大きな圧力等がかかっても、十分なシール性能を有し、閉塞が確実となる。66℃圧縮応力比率は、ISO14126(JIS K7018)に準拠して、温度66℃で測定するものである。66℃圧縮応力比率は、より好ましくは8倍以上、更に好ましくは10倍以上である。66℃圧縮応力比率は、上限値が特にないが、通常200倍以下、多くの場合150倍以下である。なお、66℃圧縮応力比率が5倍以上である本発明のダウンホールツール用分解性ゴム部材は、多くの場合、他の温度、例えば室温~177℃のような温度範囲においても、圧縮ひずみ5%における圧縮応力に対する、圧縮ひずみ70%における圧縮応力の比率が5倍以上であれば、上記の広い温度範囲においてシール機能等を果たすことができるので、より望ましいものとなる。ただし、上記の温度範囲の一部、例えば温度149℃において、上記の圧縮応力の比率が5倍未満であるようなダウンホールツール用分解性ゴム部材でも、66℃圧縮応力比率が5倍以上であれば、実用性があるダウンホールツール用分解性ゴム部材である。
〔曲げ弾性率〕
本発明のダウンホールツール用分解性シール部材(分解性ゴム部材)は、多様なダウンホール環境において、シール機能を確実に発揮する観点から、所望によっては、温度23℃における曲げ弾性率が0.005~10GPaの範囲であるものとすることができる。本発明のダウンホールツール用分解性シール部材の温度23℃における曲げ弾性率が0.005~10GPaの範囲であれば、ダウンホール環境、例えば、温度177℃、163℃、149℃、121℃、93℃、80℃または66℃、更には25~40℃などの環境内において坑井孔の閉塞を行う、例えば、ダウンホールツールとケーシングとの間の流体をシールしようとする場合、該ダウンホール環境内ではダウンホールツール用分解性シール部材の曲げ弾性率が適度に低下するため、ダウンホールツール用分解性シール部材(分解性ゴム部材)が、ダウンホールツールの形状及びケーシングの形状に確実に係合するように変形することができる。したがって、ダウンホールツール用分解性シール部材とケーシングとの当接面積が大きくなり、閉塞が確実となる。さらに、例えばフラクチャリング等のシールが必要とされる処理を実施するために、流体による極めて高い圧力が負荷されても、流体のシール(分解性保護部材については保護)が破壊されにくい効果がある。温度23℃における曲げ弾性率は、JIS7113(ISO178に相当)に準拠して測定する。
〔ダウンホール環境内でのゴム部材の分解〕
本発明のダウンホールツール用分解性シール部材(分解性ゴム部材)は、分解性ゴムに所定量の分解促進剤を含有するゴム材料から形成されるものから選択することにより、既に説明したダウンホール環境〔深度の多様化等に付随して、多くは60℃(140度F)~204℃(400度F)程度の温度であり、近年は更に25~40℃程度の低温のダウンホール環境もある。〕において、数時間~数週間以内で、所望によっては数日間以内で、該分解促進剤により促進される分解性ゴムの分解に由来して、ダウンホールツール用分解性シール部材がシール機能を喪失してシールを解除するものとすることができる。ダウンホールツール用分解性保護部材については、センサーや流路等に対する保護を解除して、露出したセンサーや流路等が本来の機能を発揮することができる。
〔ダウンホールツール用分解性ゴム部材の形状及び大きさ〕
本発明のダウンホールツール用分解性ゴム部材の形状及び大きさは、特に限定されず、ダウンホールツール用分解性シール部材やダウンホールツール用分解性保護部材等のダウンホールツール用分解性ゴム部材を備えるダウンホールツールの種類、形状や大きさに適合するように調製することができる。例えば、ダウンホールツール用分解性シール部材については、シート状(薄いフィルム状、厚板状等)、棒状(丸棒状、角柱状等)、直方体状(立方状を含む)、ボール状、その他の塊状(定形、不定形等)などの形状でもよい。本発明のダウンホールツール用分解性シール部材がシート状であったり、シーリング材またはパッキング材(詰め物様)であったりする場合は、必ずしも所定の形状を有する成形体である必要はない。また、本発明のダウンホールツール用分解性シール部材を備えるダウンホールツールが、坑井掘削用プラグ等である場合は、環状の成形体であるダウンホールツール用分解性シール部材とすることができ、更に具体的には、環状の成形体がダウンホールツールに備えられるマンドレルの軸方向と直交する外周面上に置かれるものであるダウンホールツール用分解性シール部材などとすることができ、フラックプラグまたはブリッジプラグ等の坑井掘削用プラグに備えられるダウンホールツール用分解性シール部材とすることができ、また、ボールまたはボールシートであるダウンホールツール用分解性シール部材とすることができる。同様に、ダウンホールツール用分解性保護部材についても、保護の対象であるセンサーや流路等の形状や大きさを踏まえて、シート状、センサー等の形状に対応する所定の形状、更には不定形のものでもよく、必要に応じた大きさに調製することができる。
5.ダウンホールツール用分解性ゴム部材の製造方法
本発明のダウンホールツール用分解性シール部材等のダウンホールツール用分解性ゴム部材は、製造方法が特に限定されるものではない。例えば、射出成形、押出成形(固化押出成形を含む。)、遠心成形、圧縮成形その他の公知の成形方法により、所定量の分解促進剤、分解性ゴム、及び所望により含有させる他の配合成分を含有するゴム材料である組成物を成形原料として、所定形状の成形品を成形し、または適宜形状(例えば、棒状体や厚板等)の予備成形品を成形した後、必要に応じて切削加工や穿孔等の機械加工した後に、それ自体公知の方法によって組み合わせて、ダウンホールツール用分解性ゴム部材を得ることができる。
II.ダウンホールツール
本発明によれば、前記のダウンホールツール用分解性ゴム部材を備えるダウンホールツールが提供される。ダウンホールツールの種類、形状や大きさは、特に限定されない。例えば、本発明のダウンホールツール用分解性ゴム部材は、スリーブシステム(フラックスリーブ)におけるシール部材、ダウンホールツール内におけるボールバルブ、フラッパーバルブ等のシール部材、ダウンホールツールとケーシングの間の開口部に配置されることで一時的に流体を遮断できるシール部材、更に金属製のダウンホールツール部材、センサーや流路等を覆って保護やシールを行う形で存在し、これら金属部分等が拡径することで坑井孔をシールするなどの他の多くのシール用途におけるシール部材として、または保護部材として使用することができる。本発明のダウンホールツール用分解性ゴム部材の特性である分解性に由来する崩壊性をより有効に発揮することができる観点から、好ましいダウンホールツールとしては、坑井掘削用プラグが挙げられ、より好ましくはフラックプラグまたはブリッジプラグが挙げられる。
〔坑井掘削用プラグ〕
本発明のダウンホールツール用分解性ゴム部材を備えるダウンホールツール(以下、「本発明のダウンホールツール」ということがある。)として、より好ましい坑井掘削用プラグは、通常、マンドレル(中実でも中空部を有するものでもよい。)と、マンドレルの軸方向に直交する外周面上に置かれる種々のダウンホールツール部材とを備える、それ自体周知の構造を備えるものが適合する。ダウンホールツール部材としては、拡径してダウンホールツール(坑井掘削用プラグ)とケーシングとの間の空間を閉塞して流体をシールすることができる拡径可能な環状のシール部材、及び/または、拡径してダウンホールツール(坑井掘削用プラグ)とケーシングとを相互に固定するスリップや、ウエッジ、リングその他の部材が挙げられ、それ自体周知の部材(例えば、センサー等)を備えるものとすることができる。
〔ダウンホールツールによるダウンホールのシール〕
ダウンホールツールの流体シールを確実なものとするために、本発明のダウンホールツール用分解性シール部材(分解性ゴム部材)は、例えば環状の成形体として、好ましくはダウンホールツールに備えられるマンドレルの軸方向と直交する外周面上に置かれる環状の成形体として、軸方向に圧縮されて縮径することに伴い軸方向と直交する方向に拡径する部材として、また例えばボールまたはボールシートとして、坑井孔のケーシングとダウンホールツールとの間の空間を閉塞し、流体をシールするものとすることができる。
III.坑井掘削方法
本発明のダウンホールツール用分解性ゴム部材を使用する坑井掘削方法、例えばダウンホールツール用分解性シール部材を備える坑井掘削用プラグ等のダウンホールツールを使用して、ダウンホールツールとケーシングとの間の流体をシールする坑井掘削方法によれば、並びに、本発明のダウンホールツール用分解性ゴム部材を使用して、例えばダウンホールツール用分解性シール部材を備える坑井掘削用プラグ等のダウンホールツールを使用して、坑井孔の目止め処理を行った後に、ダウンホールツールが分解される、具体的には、ダウンホールツール用分解性シール部材を備える坑井掘削用プラグ等のダウンホールツールの一部または全部が分解される坑井掘削方法によれば、所定の諸区画のフラクチャリングが終了し、または、坑井の掘削が終了して坑井が完成し、石油や天然ガス等の生産を開始するときには、坑井孔を閉塞しているダウンホールツール用分解性シール部材によるシールを、当該のダウンホール環境において所望する期間内に、容易にシール解除することができるように設計することができる。同様に、ダウンホールツール用分解性保護部材を備えるダウンホールツールを使用する坑井掘削方法においても、当該のダウンホール環境において所望する期間内に、センサーや流路等に対する保護を解除することができるように設計することができる。この結果、本発明の坑井掘削方法によれば、従来、坑井処理の終了後または坑井完成後に、シール解除を行うためにシール機能を喪失させる操作や、保護部材による保護を解除する操作のために、更には、坑井内に残置されていた多数の坑井掘削用プラグまたはシール部材や保護部材等の部材を、破砕、穿孔その他の方法によって破壊したり、小片化したりするために要していた多くの経費と時間が不要となるので、坑井掘削の経費軽減や工程短縮ができる。
〔坑井孔の閉塞〕
シール及びシールの解除について更に説明すると、本発明のダウンホールツールは、ダウンホールツール用分解性シール部材に対して、例えば、1対のリングにマンドレルの軸方向の力を加えることにより、ダウンホールツール用分解性シール部材が、軸方向に圧縮されて縮径することに伴い、マンドレルの軸方向と直交する方向に拡径して、軸方向に直交する方向の外方部がダウンホールの内壁と当接するとともに、軸方向に直交する方向の内方部がマンドレルの外周面に当接することにより、ダウンホールツールとダウンホールとの間の空間を閉塞し、流体をシールすることができる。なお、ダウンホールツール用分解性ゴム部材が短時間で分解してしまうような高温環境にあるダウンホール内において、上記した閉塞(シール)や、ダウンホールツールの保護等を行う場合には、地上から流体を注入して(cooldown injection)、ダウンホールツール用分解性ゴム部材の周辺温度を低下させた状態にコントロールすることによって、所望の時間、シール性能(強度等)や保護機能を維持するような処理方法を採用することができる。
〔ダウンホールツールの分解〕
本発明の坑井掘削用プラグ等のダウンホールツールは、所定の諸区画のフラクチャリングが終了した後、通常は、坑井の掘削が終了して坑井が完成し、石油や天然ガス等の生産を開始するときに、生分解、加水分解または更に他の何らかの方法による化学的な分解や溶剤への溶解のみならず、分解促進剤を崩壊させることができる多様な手段により、ダウンホールツール用分解性シール部材のシール機能を喪失させ、更に所望により、分解性を有するマンドレルやスリップ、リング等のダウンホールツール用分解性シール部材以外の他のダウンホールツール部材とともに、容易に分解または崩壊させて除去することができる。すなわち、本発明のダウンホールツール用分解性シール部材を使用して坑井孔の目止め処理を行った後に、ダウンホールツール用分解性シール部材がシール機能を喪失し、更に所望により分解されることによって、(i)坑井内において流体の移動を妨げるためのシールが所望期間内に解除できる、(ii)生産を妨げる不要なダウンホールツールの除去が容易となる、(iii)ダウンホールツールに備えられる他の部材をPGAやPLA等の分解性材料、より好ましくはPGAから形成することによれば、生産開始前にダウンホールツールやダウンホールツール部材の破砕処理が全く不要であるダウンホールツールを得ることができる、(iv)フラクチャリング工程に使用されるダウンホールツールに限られることなく、何らかのシールが必要とされる多様な工程において使用される種々のダウンホールツールに適用することができる、などの利点がある。本発明のダウンホールツール用分解性保護部材を使用してセンサー等の保護を行う坑井掘削方法についても、同様の利点がある。なお、坑井処理が終了した後に残存するダウンホールツール用分解性ゴム部材は、生産を開始するまでに完全に消失していることが好ましいが、完全に消失していないとしても、強度が低下してダウンホール中の水流等の刺激により崩壊するような状態となれば、崩壊したダウンホールツール用分解性ゴム部材は、フローバックなどにより容易に回収することができ、ダウンホールやフラクチャに目詰まりを生じさせることがないので、石油や天然ガス等の生産障害となることがない。また通常、ダウンホールの温度が高い方が、短時間でダウンホールツール用分解性ゴム部材の分解や強度低下が進行する。なお、坑井によっては地層中の含水量が低いことがあり、その場合にはフラクチャリング時に使用した水ベースの流体を、フラクチャリング後に回収することなく坑井中に残留させることで、ダウンホールツールの分解を促進させることができる。
Claims (32)
- 分解性ゴム100質量部に対して分解促進剤0.1~20質量部を含有するゴム材料から形成されることを特徴とするダウンホールツール用分解性ゴム部材。
- 分解性ゴム100質量部に対して分解促進剤0.1~20質量部を含有するゴム材料から形成され、温度150℃の水に24時間浸漬後の質量または50%ひずみ圧縮応力の、浸漬前の質量または50%ひずみ圧縮応力に対する減少率が5%以上であることを特徴とするダウンホールツール用分解性ゴム部材。
- 温度150℃の水に72時間浸漬後の質量の、浸漬前の質量に対する減少率が5~100%である請求項2記載のダウンホールツール用分解性ゴム部材。
- 分解性ゴム100質量部に対して分解促進剤0.1~20質量部を含有するゴム材料から形成され、温度150℃の水に72時間浸漬後の質量の、浸漬前の質量に対する減少率が5~100%であることを特徴とするダウンホールツール用分解性ゴム部材。
- 温度66℃における引張破断ひずみが50%以上、70%ひずみ圧縮応力が10MPa以上かつ圧縮破断ひずみが50%以上である請求項1乃至4のいずれか1項に記載のダウンホールツール用分解性ゴム部材。
- 表面硬度がA60~D80の範囲内である請求項5記載のダウンホールツール用分解性ゴム部材。
- 温度66℃において、圧縮ひずみ5%における圧縮応力に対する、圧縮ひずみ70%における圧縮応力の比率が5倍以上である請求項1乃至6のいずれか1項に記載のダウンホールツール用分解性ゴム部材。
- ドライ環境下で安定であり、温度23℃の水に6時間浸漬後の50%ひずみ圧縮応力の、1時間浸漬後の50%ひずみ圧縮応力に対する減少率が5%未満である請求項1乃至7のいずれか1項に記載のダウンホールツール用分解性ゴム部材。
- 分解促進剤が酸性物質である請求項1乃至8のいずれか1項に記載のダウンホールツール用分解性ゴム部材。
- 酸性物質が酸生成物質である請求項9記載のダウンホールツール用分解性ゴム部材。
- 分解促進剤が可塑剤である請求項1乃至8のいずれか1項に記載のダウンホールツール用分解性ゴム部材。
- 分解促進剤が、有機酸、無機酸、有機酸エステル、無機酸エステル及び酸無水物からなる群より選ばれる少なくとも1種を含有する請求項1乃至8のいずれか1項に記載のダウンホールツール用分解性ゴム部材。
- 分解促進剤が、グリコリド、ラクチド、ε-カプロラクトン、ポリグリコール酸、ポリ乳酸、p-トルエンスルホン酸メチル及び3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物からなる群より選ばれる少なくとも1種を含有する請求項1乃至8のいずれか1項に記載のダウンホールツール用分解性ゴム部材。
- 分解性ゴムは、ウレタンゴム、天然ゴム、イソプレンゴム、エチレンプロピレンゴム、ブチルゴム、スチレンゴム、アクリルゴム、脂肪族ポリエステルゴム、クロロプレンゴム、ポリエステル系熱可塑性エラストマー及びポリアミド系熱可塑性エラストマーからなる群より選ばれる少なくとも1種を含有する請求項1乃至13のいずれか1項に記載のダウンホールツール用分解性ゴム部材。
- 分解性ゴムは、加水分解性の官能基を有するゴムを含有する請求項1乃至14のいずれか1項に記載のダウンホールツール用分解性ゴム部材。
- ゴム材料は、強化材を含有する請求項1乃至15のいずれか1項に記載のダウンホールツール用分解性ゴム部材。
- 温度23℃における曲げ弾性率が0.005~10GPaの範囲である請求項1乃至16のいずれか1項に記載のダウンホールツール用分解性ゴム部材。
- シール部材である請求項1乃至17のいずれか1項に記載のダウンホールツール用分解性ゴム部材。
- 環状の成形体である請求項18記載のダウンホールツール用分解性ゴム部材。
- 環状の成形体が、ダウンホールツールに備えられるマンドレルの軸方向と直交する外周面上に置かれるものである請求項19記載のダウンホールツール用分解性ゴム部材。
- ボールまたはボールシートである請求項1乃至17のいずれか1項に記載のダウンホールツール用分解性ゴム部材。
- ダウンホールツール用分解性保護部材である請求項1乃至17のいずれか1項に記載のダウンホールツール用分解性ゴム部材。
- 坑井掘削用プラグに備えられる請求項1乃至22のいずれか1項に記載のダウンホールツール用分解性ゴム部材。
- 請求項1乃至23のいずれか1項に記載のダウンホールツール用分解性ゴム部材を備えるダウンホールツール。
- 坑井掘削用プラグである請求項24記載のダウンホールツール。
- 請求項1乃至23のいずれか1項に記載のダウンホールツール用分解性ゴム部材を使用する坑井掘削方法。
- 請求項1乃至23のいずれか1項に記載のダウンホールツール用分解性ゴム部材を使用して、ダウンホールツールとケーシングとの間の流体をシールする坑井掘削方法。
- 請求項1乃至23のいずれか1項に記載のダウンホールツール用分解性ゴム部材を使用して、坑井孔の目止め処理を行った後に、ダウンホールツールが分解される坑井掘削方法。
- 請求項1乃至23のいずれか1項に記載のダウンホールツール用分解性ゴム部材を備えるダウンホールツールを使用して、坑井孔をシールした後に、坑井孔内で該ダウンホールツール用分解性ゴム部材が分解されることを特徴とする坑井掘削方法。
- 請求項1乃至23のいずれか1項に記載のダウンホールツール用分解性ゴム部材を備え、
さらに分解性材料を含有する他のダウンホールツール用部材を備えるダウンホールツールを使用して、坑井孔をシールした後に、坑井孔内で該ダウンホールツール用分解性ゴム部材が分解されることを特徴とする坑井掘削方法。 - 他のダウンホールツール用部材に含有される分解性材料がポリグリコール酸である請求項30記載の坑井掘削方法。
- 請求項1乃至23のいずれか1項に記載のダウンホールツール用分解性ゴム部材を備え、該ダウンホールツール用分解性ゴム部材が、他のダウンホールツール用部材に接する、及び/または、他のダウンホールツール用部材を覆うように配置されてなるダウンホールツールを使用して、坑井処理を行った後に、坑井孔内で該ダウンホールツール用分解性ゴム部材が分解されることを特徴とする坑井掘削方法。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201580010065.7A CN106030023B (zh) | 2014-03-07 | 2015-03-04 | 钻井工具用分解性橡胶构件、分解性密封构件、分解性保护构件、钻井工具、以及钻井方法 |
| CA2941718A CA2941718C (en) | 2014-03-07 | 2015-03-04 | Degradable rubber member for downhole tools, degradable seal member, degradable protecting member, downhole tool, and method for well drilling |
| EP15757709.9A EP3115544B1 (en) | 2014-03-07 | 2015-03-04 | Degradable rubber member for downhole tool, degradable seal member, degradable protective member, downhole tool, and well-drilling method |
| JP2016506538A JP6114875B2 (ja) | 2014-03-07 | 2015-03-04 | ダウンホールツール用分解性ゴム部材、分解性シール部材、分解性保護部材、ダウンホールツール、及び坑井掘削方法 |
| US15/123,857 US10280699B2 (en) | 2014-03-07 | 2015-03-04 | Degradable rubber member for downhole tools, degradable seal member, degradable protecting member, downhole tool, and method for well drilling |
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| JP2014044611 | 2014-03-07 | ||
| JP2014-044611 | 2014-03-07 | ||
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| US (1) | US10280699B2 (ja) |
| EP (1) | EP3115544B1 (ja) |
| JP (1) | JP6114875B2 (ja) |
| CN (4) | CN110242244B (ja) |
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| EP3015501A4 (en) * | 2013-06-28 | 2016-10-26 | Kureha Corp | RUBBER ELEMENT FOR DRILLING TOOLS, DRILLING TOOL AND METHOD FOR RECOVERING HYDROCARBON RESOURCES |
| WO2017110609A1 (ja) | 2015-12-22 | 2017-06-29 | 株式会社クレハ | 組成物、ダウンホールツール用組成物、ダウンホールツール用分解性ゴム部材、ダウンホールツール、及び坑井掘削方法 |
| EP3395879A4 (en) * | 2015-12-25 | 2018-12-12 | Kureha Corporation | Composition, composition for downhole tool, degradable rubber member for downhole tool, downhole tool, and well drilling method |
| US20200071486A1 (en) * | 2017-05-25 | 2020-03-05 | Kureha Corporation | Rubber composition for downhole tools and member for downhole tools |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3015501A4 (en) * | 2013-06-28 | 2016-10-26 | Kureha Corp | RUBBER ELEMENT FOR DRILLING TOOLS, DRILLING TOOL AND METHOD FOR RECOVERING HYDROCARBON RESOURCES |
| US10414851B2 (en) | 2013-06-28 | 2019-09-17 | Kureha Corporation | Rubber member for downhole tools, downhole tool, and method for recovering hydrocarbon resource |
| WO2017110609A1 (ja) | 2015-12-22 | 2017-06-29 | 株式会社クレハ | 組成物、ダウンホールツール用組成物、ダウンホールツール用分解性ゴム部材、ダウンホールツール、及び坑井掘削方法 |
| JP2017114989A (ja) * | 2015-12-22 | 2017-06-29 | 株式会社クレハ | 組成物、ダウンホールツール用組成物、ダウンホールツール用分解性ゴム部材、ダウンホールツール、及び坑井掘削方法 |
| CN108368309A (zh) * | 2015-12-22 | 2018-08-03 | 株式会社吴羽 | 组合物、井下工具用组合物、井下工具用分解性橡胶构件、井下工具、以及坑井挖掘方法 |
| US10815362B2 (en) | 2015-12-22 | 2020-10-27 | Kureha Corporation | Composition, composition for downhole tools, degradable rubber member for downhole, downhole tool, and method for well drilling |
| CN108368309B (zh) * | 2015-12-22 | 2021-04-20 | 株式会社吴羽 | 组合物、井下工具用组合物、井下工具用分解性橡胶构件、井下工具、以及坑井挖掘方法 |
| EP3395879A4 (en) * | 2015-12-25 | 2018-12-12 | Kureha Corporation | Composition, composition for downhole tool, degradable rubber member for downhole tool, downhole tool, and well drilling method |
| US10829614B2 (en) | 2015-12-25 | 2020-11-10 | Kureha Corporation | Composition, composition for downhole tools, degradable rubber member for downhole, downhole tool, and method for well drilling |
| US20200071486A1 (en) * | 2017-05-25 | 2020-03-05 | Kureha Corporation | Rubber composition for downhole tools and member for downhole tools |
| US11059952B2 (en) | 2017-05-25 | 2021-07-13 | Kureha Corporation | Rubber composition for downhole tools and member for downhole tools |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106030023B (zh) | 2019-07-30 |
| CN110294876A (zh) | 2019-10-01 |
| EP3115544A1 (en) | 2017-01-11 |
| CN106030023A (zh) | 2016-10-12 |
| CN110242244B (zh) | 2021-09-07 |
| CA2941718C (en) | 2017-10-17 |
| US20170016298A1 (en) | 2017-01-19 |
| CN110242244A (zh) | 2019-09-17 |
| CN110294876B (zh) | 2021-09-21 |
| CA2941718A1 (en) | 2015-09-11 |
| CN110318699B (zh) | 2021-12-07 |
| EP3115544B1 (en) | 2020-10-14 |
| US10280699B2 (en) | 2019-05-07 |
| JP6114875B2 (ja) | 2017-04-12 |
| JPWO2015133545A1 (ja) | 2017-04-06 |
| EP3115544A4 (en) | 2017-04-05 |
| CN110318699A (zh) | 2019-10-11 |
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