WO2023053955A1 - 樹脂組成物、ダウンホールツールまたはその部材、プラグおよび坑井処理方法 - Google Patents
樹脂組成物、ダウンホールツールまたはその部材、プラグおよび坑井処理方法 Download PDFInfo
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- WO2023053955A1 WO2023053955A1 PCT/JP2022/034307 JP2022034307W WO2023053955A1 WO 2023053955 A1 WO2023053955 A1 WO 2023053955A1 JP 2022034307 W JP2022034307 W JP 2022034307W WO 2023053955 A1 WO2023053955 A1 WO 2023053955A1
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- Prior art keywords
- plug
- mass
- parts
- downhole tool
- opening
- Prior art date
Links
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Images
Classifications
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- 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
-
- 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
Definitions
- the present invention relates to a resin composition, a downhole tool or its member, a plug, and a well treatment method.
- Downholes underground drilling holes
- hydrocarbon resources such as oil and gas from the ground
- downhole tools and downhole tool components are used.
- Downhole tools and downhole tool components are typically disposed of by collapsing in situ downhole or by dropping, and thus may be constructed of degradable polymers.
- Downhole tool members made of such degradable polymers are known, for example, downhole tool members made of polyglycolic acid.
- Polyglycolic acid has high strength and is hydrolyzable, so it is suitably used as a material for downhole tools or members thereof (see, for example, Patent Document 1).
- the material of the downhole tool or its members is a resin composition that quickly decomposes after retaining the weight and shape of the resin for a certain period of time in hot water at a temperature higher than 135 ° C., which is required for oil field drilling technology. is known (see, for example, Patent Document 2).
- a resin composition a resin composition containing a polyester and a cyclic carbodiimide compound is known (see, for example, Patent Document 3).
- the resin composition as a material for the molded product includes 100 parts by mass of an aliphatic polyester containing 50% by mass or more of polyglycolic acid, and an aliphatic polyester resin composition containing 1 to 30 parts by mass of a carboxylic acid anhydride. Moldings formed from are known. The molded article is known to exhibit excellent degradability even in a downhole environment at a relatively low temperature of less than 66° C. (see, for example, Patent Document 4).
- a resin composition containing polyglycolic acid is useful as a material for downhole tools or their members from the viewpoint of strength and hydrolyzability.
- the higher the ambient temperature the more rapidly the thickness of the downhole tool or its members tends to decrease due to the hydrolysis of polyglycolic acid. Therefore, a downhole tool or a member thereof containing polyglycolic acid as its material may not be able to maintain its usage pattern for a desired period of time, especially in a well at high temperature (for example, 80° C.).
- An object of one aspect of the present invention is to provide a technique capable of suppressing reduction in thickness of a downhole tool or its members in a high-temperature wellbore.
- a resin composition according to an aspect of the present invention comprises 50 parts by mass or more and 97 parts by mass or less of polyglycolic acid, 3 parts by mass or more and 50 parts by mass or less of polybutylene terephthalate, 2 parts by mass or more and 15 parts by mass or less of a cyclic carbodiimide compound with respect to 100 parts by mass of the total amount of polyglycolic acid and the polybutylene terephthalate.
- a downhaul tool or a member thereof includes a resin molded body formed by molding using the above resin composition as a raw material.
- a plug according to one aspect of the present invention is a plug for temporarily blocking the flow of fluid in a well, and is the above downhole tool or its member.
- a downhole tool includes a tubular member and the plug according to any one of claims 4 to 8, wherein the tubular member has an opening communicating between the inside and outside of the tubular member on the peripheral surface of the tubular member, and the plug is engaged with the tubular member so as to block the opening.
- a well processing method uses the above plug to temporarily cut one or more regions of at least one of the well and the downhole tool. and removing the temporary sealing by the plug by decomposing the resin molding portion of the plug to change the flow path of the fluid in the region.
- a well treatment method includes installing the plug in the well to impede the flow of fluid in the well, and disintegrating the shaped body to restore said fluid flow.
- a well processing method includes a first opening at one end, a second opening at the other end, and a gap between the one end and the other end.
- FIG. 4 is a schematic view of a cross-section of a downhole plug while plugging a wellbore according to an embodiment of the present invention; It is a figure for demonstrating the observation position of the microscopic structure of a resin molding.
- FIG. 4 is a SEM photograph showing the state of dispersion of resin in the cross section of a resin molded article having a mass ratio of PGA:PBT of 90:10.
- FIG. 10 is a SEM photograph showing the state of dispersion of resin in the cross section of a resin molding having a mass ratio of PGA:PBT of 70:30.
- FIG. 4 is a SEM photograph showing the state of dispersion of resin in the cross section of a resin molding having a mass ratio of PGA:PBT of 70:30.
- FIG. 10 is a SEM photograph showing the state of dispersion of resin in the cross section of a resin molding having a mass ratio of PGA:PBT:cyc-CDI of 70:30:5.
- FIG. 10 is a SEM photograph showing the state of dispersion of resin in the cross section of a resin molding having a mass ratio of PGA:PET of 70:30.
- FIG. 4 is a SEM photograph showing the state of dispersion of resin in the cross section of a resin molded article having a mass ratio of PGA:PET:cyc-CDI of 70:30:5.
- a resin composition according to one embodiment of the present invention contains polyglycolic acid, polybutylene terephthalate, and a cyclic carbodiimide compound.
- Polyglycolic acid (PGA) Polyglycolic acid in the present embodiment is a polymer containing repeating units represented by -(-O-CH 2 -CO-)-. Polyglycolic acid is preferably a homopolymer of glycolic acid, but may be a copolymer of glycolic acid and other monomer components.
- polyglycolic acid When polyglycolic acid is a copolymer, other monomer components include, for example, L-lactic acid, D-lactic acid, hydroxycarboxylic acids such as 3-hydroxybutanoic acid and 1-hydroxyhexanoic acid, and 1,4-butane.
- An ester compound composed of a diol and a dicarboxylic acid such as a condensate of a diol and succinic acid and a condensate of 1,4-butanediol and adipic acid, produced by intramolecular condensation of the above-mentioned other monomer components Cyclic esters and lactones, and cyclic carbonates such as trimethylene carbonate are included.
- the constituent units derived from glycolic acid are 70 mol% or more, preferably 80 mol% or more, and more preferably 90 mol% or more.
- the melt viscosity of the copolymer is preferably lower than that of a homopolymer of glycolic acid having the same molecular weight as the copolymer.
- a copolymer having such a melt viscosity there is no need to raise the melting temperature of the resin composition. Therefore, it is possible to suppress the decrease in the molecular weight of polyglycolic acid due to the decomposition of the constituent units derived from glycolic acid. Therefore, it is preferable from the viewpoint of increasing the strength of a resin molded article obtained by molding the resin composition.
- the molecular weight of polyglycolic acid may be determined as appropriate within the range in which the effects of the embodiments of the present invention can be obtained.
- the molecular weight of polyglycolic acid is preferably more than 20,000 in terms of weight average molecular weight, from the viewpoint of exhibiting water vapor barrier properties due to polyglycolic acid in resin moldings.
- the molecular weight of polyglycolic acid is more preferably 70,000 or more, and still more preferably 150,000 or more.
- the upper limit of the molecular weight of polyglycolic acid is not particularly limited, but from the viewpoint of enabling solidification extrusion molding or injection molding, the weight average molecular weight is usually preferably 500,000 or less, more preferably 300,000 or less.
- Polybutylene terephthalate (PBT) Polybutylene terephthalate in the embodiment of the present invention is polyester having a structure in which terephthalic acid units and 1,4-butanediol units are ester-bonded.
- Polybutylene terephthalate is preferably a homopolymer (homopolymer) of polybutylene terephthalate obtained by polycondensation of terephthalic acid and 1,4-butanediol, but may be a copolymer or a mixture thereof. good.
- polybutylene terephthalate may contain dicarboxylic acid units other than terephthalic acid.
- dicarboxylic acids include aromatic dicarboxylic acids, alicyclic dicarboxylic acids and aliphatic dicarboxylic acids other than terephthalic acid.
- aromatic dicarboxylic acids include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl -3,3′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, bis(4,4′-carboxyphenyl)methane, anthracene dicarboxylic acid and 4,4′-diphenyl ether dicarboxylic acid.
- alicyclic dicarboxylic acids examples include 1,4-cyclohexanedicarboxylic acid and 4,4'-dicyclohexyldicarboxylic acid.
- aliphatic dicarboxylic acids examples include adipic acid, sebacic acid, azelaic acid and dimer acid.
- polybutylene terephthalate may contain other diol units in addition to 1,4-butanediol.
- diol units include aliphatic or alicyclic diols having 2 to 20 carbon atoms, bisphenol derivatives, and the like. More specific examples of other diol units include ethylene glycol, propylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, cyclohexanedimethanol, 4,4'. -dicyclohexylhydroxymethane, 4,4'-dicyclohexylhydroxypropane and ethylene oxide addition diols of bisphenol A.
- polybutylene terephthalate is derived from a trifunctional monomer for introducing a branched structure, a monomer having four or more functional groups, or a monofunctional compound for molecular weight control, in addition to the above bifunctional monomers.
- trifunctional monomers include trimellitic acid, trimesic acid, pyromellitic acid and trimethylolpropane.
- tetrafunctional monomers include pentaerythritol.
- hexafunctional monomers include dipentaerythritol.
- the polybutylene terephthalate in the embodiment of the present invention may be polybutylene terephthalate modified by copolymerization.
- modified polybutylene terephthalates include polyester ethers copolymerized with polyalkylene glycols, particularly polytetramethylene glycol, dimer acid-copolymerized polybutylene terephthalate, and isophthalic acid-copolymerized polybutylene terephthalate. included.
- Modified polybutylene terephthalate refers to a polybutylene terephthalate in which the amount of copolymer is 1 mol % or more and less than 50 mol % of all segments of polybutylene terephthalate.
- the amount of terminal carboxyl groups of polybutylene terephthalate may be selected and determined as appropriate.
- the amount of terminal carboxyl groups of polybutylene terephthalate may be 60 eq/ton or less, preferably 50 eq/ton or less, more preferably 30 eq/ton or less, from the viewpoint of alkali resistance and hydrolysis resistance.
- the terminal carboxyl group content of polybutylene terephthalate may be 10 eq/ton from the viewpoint of productivity in the production of polybutylene terephthalate.
- the terminal carboxyl group content of polybutylene terephthalate can be measured by dissolving 0.5 g of polybutylene terephthalate resin in 25 mL of benzyl alcohol and titrating with a 0.01 mol/L benzyl alcohol solution of sodium hydroxide. .
- the amount of terminal carboxyl groups can be appropriately adjusted according to conventionally known production conditions such as the charging ratio of raw materials at the time of polymerization.
- the intrinsic viscosity of polybutylene terephthalate in the embodiment of the present invention is preferably 0.5 to 2 dL/g, more preferably 0.6 to 1.5 dL/g, from the viewpoint of moldability and mechanical properties. more preferred.
- the intrinsic viscosity can be measured at 30° C. in a 1:1 (mass ratio) mixed solvent of tetrachloroethane and phenol.
- the polybutylene terephthalate of the embodiment of the present invention may be a commercial product or a synthetic product.
- commercially available products include "Novaduran” (registered trademark) manufactured by Mitsubishi Engineering-Plastics Corporation.
- the synthetic product is produced by melt-polymerizing a dicarboxylic acid component or an ester derivative thereof containing terephthalic acid as a main component and a diol component containing 1,4-butanediol as a main component in a batchwise or continuous manner by a known method. It is possible to manufacture
- the molecular weight of the polybutylene terephthalate in the embodiment of the invention may be appropriately determined within the range in which the effects of the embodiment of the invention can be obtained. If the molecular weight of the polybutylene terephthalate is too small, the effect of suppressing the entry of water into the resin molding may be insufficient, and if it is too large, the dispersibility in the resin molding may be poor. From the viewpoint of water intrusion suppression effect, the weight-average molecular weight of polybutylene terephthalate is preferably 5,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more.
- the weight-average molecular weight of polybutylene terephthalate is preferably 50,000 or less, more preferably 30,000 or less. , is more preferably 20,000 or less.
- the ratio M T /M A of the weight average molecular weight M T of polybutylene terephthalate to the weight average molecular weight M A of polyglycolic acid is preferably 0.01 or more from the viewpoint of further enhancing the effect of suppressing water intrusion. , is more preferably 0.02 or more, and more preferably 0.03 or more.
- M T /M A is preferably 1.0 or less, more preferably 0.8 or less, and 0.3 or less. It is even more preferable to have When M T /M A is sufficiently small, polybutylene terephthalate tends to be sufficiently uniformly and finely dispersed in polyglycolic acid.
- the weight average molecular weights of PGA and PBT can be measured by known methods such as gel permeation chromatography (GPC), but may be catalog values.
- the cyclic carbodiimide compound contained in the polyglycolic acid resin composition of the present embodiment is a compound having a cyclic structure in which the first nitrogen and the second nitrogen of the carbodiimide group are linked by a linking group.
- a cyclic carbodiimide compound can be represented, for example, by the following formula (I).
- R represents one or more divalent bonding groups selected from the group consisting of aliphatic groups, alicyclic groups and aromatic groups. Moreover, in formula (I), R may contain a heteroatom. Examples of heteroatoms include oxygen (O), nitrogen (N), sulfur (S) and phosphorus (P). Furthermore, R may contain a ring structure, and the ring structure may contain a carbodiimide structure.
- a cyclic carbodiimide compound has two cyclic structures in which the first nitrogen and the second nitrogen of the carbodiimide group are linked by a linking group, and these cyclic structures share some carbon atoms.
- the type and number of atoms constituting the main chain of the cyclic structure can be appropriately determined within the range in which the effects of the present embodiment can be obtained.
- the number of atoms directly constituting the cyclic structure is preferably 8 or more, more preferably 10 or more.
- the number of atoms is preferably 50 or less, more preferably 20 or less.
- R may further have a monovalent substituent as long as the effects of the present embodiment can be obtained. More specifically, R is a divalent to tetravalent aliphatic group having 1 to 20 carbon atoms, a divalent to tetravalent alicyclic group having 3 to 20 carbon atoms, a divalent to tetravalent aromatic group having 5 to 15 carbon atoms. groups or combinations thereof. Examples of such combinations include an alkylene-arylene group in which an alkylene group and an arylene group are bonded.
- Examples of the aliphatic group for R include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms and an alkanetetrayl group having 1 to 20 carbon atoms.
- alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene and hexadecylene groups.
- alkanetriyl groups include methanetriyl, ethanetriyl, propanetriyl, butanetriyl, pentanetriyl, hexanetriyl, heptanetriyl, octanetriyl, nonanetriyl, decantriyl, dodecanetriyl yl and hexadecanetriyl groups are included.
- alkanetetrayl groups include methantetrayl, ethanetetrayl, propanetetrayl, butanetetrayl, pentanetetrayl, hexanetetrayl, heptanetetrayl, octatetrayl, nonane Tetrayl, decantetrayl, dodecanetetrayl and hexadecanetetrayl groups are included.
- Examples of the alicyclic group for R include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms and a cycloalkanetetrayl group having 3 to 20 carbon atoms.
- cycloalkylene groups include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene, cyclodecylene, cyclododecylene and cyclohexadecylene groups.
- cycloalkanetriyl groups include cyclopropanetriyl, cyclobutanetriyl, cyclopentanetriyl, cyclohexanetriyl, cycloheptanetriyl, cyclooctanetriyl, cyclononanetriyl, cyclo Included are decantriyl, cyclododecanetriyl and cyclohexadecanetriyl groups.
- cycloalkanetetrayl groups include cyclopropanetetrayl, cyclobutanetetrayl, cyclopentanetetrayl, cyclohexanetetrayl, cycloheptanetetrayl, cyclooctanetetrayl, cyclononanetetrayl, Cyclodecanetetrayl, cyclododecanetetrayl and cyclohexadecanetetrayl groups are included.
- Examples of the aromatic group for R include an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms and an arenetetrayl group having 5 to 15 carbon atoms.
- the aromatic group may contain heteroatoms.
- arylene groups include phenylene groups and naphthalenediyl groups.
- arenetriyl groups include benzenetriyl groups and naphthalenetriyl groups.
- arenetetrayl groups examples include benzenetetrayl groups and naphthalenetetrayl groups.
- R may have include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, and an ether group. and aldehyde groups.
- cyclic carbodiimide compounds it is preferable to use a compound having only one carbodiimide group in one cyclic structure from the viewpoint of preventing deterioration of the working environment due to the peculiar odor of isocyanate compounds. This is because a cyclic carbodiimide having this structure does not liberate a compound having an isocyanate group even if it reacts with a carboxyl group at the terminal of polyglycolic acid.
- Examples of the above cyclic carbodiimide compounds include compounds represented by the following formula (II) or the following formula (III).
- the cyclic carbodiimide compound when the cyclic carbodiimide compound contains multiple carbodiimide groups in the same molecular structure, it may also function as a chain extender through reaction with the carboxyl group end of the polymer. Therefore, the cyclic carbodiimide compound is a compound containing a plurality of carbodiimide groups in the same molecular structure, such as formula (III), from the viewpoint of suppressing the molecular weight reduction of polyglycolic acid due to decomposition during melt kneading at high temperature. preferred.
- the content of PGA in the resin composition of the embodiment of the present invention is 50 parts by mass or more and 97 parts by mass or less.
- the PGA content of 50 parts by mass or more is preferable from the viewpoint of sufficiently imparting rapid decomposition properties derived from PGA to the resin molding, and from the viewpoint of improving the decomposition properties, it is 55 parts by mass or more. is more preferable, and 60 parts by mass or more is even more preferable.
- the PGA content is 97 parts by mass or less from the viewpoint of sufficiently suppressing the thickness reduction rate of the resin molded body in water at 80 ° C., and from the viewpoint of suppressing the thickness reduction rate, 90 parts by mass is more preferably 80 parts by mass or less.
- the content of PBT in the resin composition of the embodiment of the present invention is 3 parts by mass or more and 50 parts by mass or less. It is preferable that the content of PBT is 3 parts by mass or more from the viewpoint of sufficiently suppressing the thickness reduction rate of the resin molded body in water at 80 ° C., and from the viewpoint of suppressing the thickness reduction rate, it is 20 parts by mass or more. more preferably 25 parts by mass or more. In addition, it is preferable that the content of PBT is 50 parts by mass or less from the viewpoint of sufficiently expressing the decomposition characteristics of the resin molding, and from the viewpoint of improving the decomposition characteristics, it is more preferable that the content is 45 parts by mass or less. , 40 parts by mass or less.
- the content of cyc-CDI in the resin composition of the embodiment of the present invention is 2 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass as the total amount of PGA and PBT. It is preferable that the content of cyc-CDI is 2 parts by mass or more with respect to 100 parts by mass of the total amount of PGA and PBT from the viewpoint of achieving both the expression of the decomposition characteristics and the effect of suppressing the thickness reduction rate. From the viewpoint of improving the inhibitory effect, it is more preferably 4 parts by mass or more, and even more preferably 5 parts by mass or more.
- the content of cyc-CDI is 15 parts by mass or less from the viewpoint of achieving both the effect of adding cyc-CDI and economy, and from the viewpoint of economy, it is preferably 10 parts by mass or less. More preferably, it is 8 parts by mass or less.
- the resin composition of the embodiment of the present invention has the above structure, so that it has a decomposition property due to PGA compared to the case where PGA is used alone without using PGA and PBT in combination, but It is possible to suppress the rate of thickness reduction in water at 80°C. This is probably because the cyc-CDI described above causes the PBT chain to be chain-extended during molding. As a result, the melt miscibility of PGA and PBT during molding is reduced, and a streak-like or network-like PBT phase is formed in the resin molded product. As a result, contact of water with the PGA phase in the resin molded product is suppressed. As a result, the decomposition delay effect as described above is considered to be exhibited.
- the resin composition of the embodiment of the present invention contains a heat stabilizer, an antioxidant, an impact modifier, a cross-linking agent, an organic filler, an inorganic filler, and a coloring agent within the range where the effects of the embodiment of the present invention can be obtained.
- Other additives such as agents may also be included.
- the form of the resin composition of the embodiment of the present invention is not limited.
- the resin composition may be a mixture of powdery raw materials, or may be a melt-kneaded product of these raw materials such as pellets.
- the terminal of PGA may be capped with a cyclic carbodiimide compound
- the terminal of PBT may be capped with a cyclic carbodiimide compound.
- the “capped structure” means a structure obtained by reacting a terminal carboxyl group of PGA or PBT with a cyclic carbodiimide compound. A portion of the ends of PGA or PBT may be capped with a cyclic carbodiimide compound.
- the resin composition of the present embodiment contains, in addition to PGA, PBT and the cyclic carbodiimide compound, for example, a cyclic carbodiimide at the terminal of PGA or PBT.
- the compound may further include a derivative of the cyclic carbodiimide compound formed by reacting and bonding.
- a resin molding is formed by molding using the resin composition of the embodiment of the present invention as a raw material.
- the resin molding can be produced by mixing PGA, PBT and cyc-CDI and solidifying the mixture by extrusion molding or injection molding.
- the mixture may be melt-kneaded and pelletized PGA, PBT and cyc-CDI.
- the temperature is preferably 220 to 280° C., more preferably 230 to 260° C., from the viewpoint of suppressing thermal decomposition of PGA.
- the temperature at which the resin molding is solidified, extruded or injection molded is preferably 220 to 280.degree. C., more preferably 230 to 260.degree.
- the resin molded article is formed from the resin composition of the embodiment of the present invention, it is preferably decomposed even in fluid or water with a low salt concentration.
- the molecular weight of PGA in the surface layer of the resin molding decreases due to hydrolysis.
- the surface layer portion of the resin molding becomes brittle.
- PGA with a reduced molecular weight is permeable to water, PGA is gradually hydrolyzed from the surface layer to the center of the resin molding. Thus, embrittlement of the resin molding progresses.
- the rate at which embrittlement progresses in a resin molded body is defined as the thickness reduction rate.
- the thickness reduction rate is the rate at which the thickness of the non-embrittled portion of the resin molding decreases. Embrittlement progresses from the surface of the resin molding toward the center, and the thickness of the non-embrittled portion decreases from the surface side. Therefore, the progress rate of embrittlement shows a positive correlation with the thickness reduction rate.
- Decomposition lead time means the time from when the resin molded body is immersed in water to when the PGA in the surface layer of the molded body is hydrolyzed and the thickness of the molded body starts to decrease.
- “embrittlement” means that the molecular weight of PGA is lowered by hydrolysis of PGA, and as a result, the resin molding becomes brittle.
- a brittle portion of the resin molding is also referred to as a brittle layer.
- the thickness reduction rate can be adjusted by the amount of PBT or the amount of cyc-CDI.
- the thickness reduction rate of the resin molded body in water at 80°C may be appropriately determined according to the application of the resin molded body.
- the thickness reduction rate in water at 80 ° C. is 0.1 ⁇ m / from the viewpoint of shape stability in a high temperature environment. hr or more is preferable, 1 ⁇ m/hr or more is more preferable, and 5 ⁇ m/hr or more is even more preferable.
- the thickness reduction rate is preferably less than 60 ⁇ m/hr, more preferably less than 35 ⁇ m/hr, and even more preferably less than 30 ⁇ m/hr.
- the resin molding in this embodiment is formed from a resin composition containing PGA, PBT and cyc-CDI as described above.
- PGA has a high water vapor barrier property. Since hydrolysis and embrittlement of the center portion of the resin molding according to the present embodiment do not occur until the surface layer portion becomes embrittled, embrittlement does not progress rapidly.
- the resin molding in this embodiment contains PBT.
- PBT also has a sufficiently high water vapor barrier property and a sufficiently low hydrolyzability compared to PGA. As shown in the examples below, when PBT is 15 parts by mass or less with respect to 100 parts by mass of PGA and PBT in total, PBT tends to be finely dispersed in the PGA phase. Since water diffuses along the interface between the PGA phase and the PBT phase, the fine dispersion of the PBT phase in the PGA phase basically contributes to the acceleration of decomposition of the PGA phase. On the other hand, as the amount of PBT added increases further, the PBT aggregates in the PGA phase and the distance between the PBT phases increases, so the length of the path for water to reach the PGA phase becomes longer.
- the resin composition of the resin molding in the present embodiment further contains cyc-CDI
- the PBT phase dispersed in the PGA phase becomes larger than when it does not contain cyc-CDI, and is distributed in a streaky or network manner. Sometimes. Therefore, diffusion of water molecules in the resin molding is further suppressed. This slows down the progress of embrittlement.
- the resin molding in this embodiment contains cyc-CDI or carbodiimide groups.
- Water molecules passing through the embrittlement layer react with cyc-CDI or carbodiimide groups, so diffusion of water molecules is further suppressed. This further retards the progress of embrittlement.
- the carbodiimide groups in the resin composition can be quantified, for example, by 1 H NMR measurement using dimethylsulfone as a standard substance.
- the resin molding in the present embodiment can delay hydrolysis and embrittlement in high-temperature water even after the decomposition lead time has elapsed. Therefore, in applications of downhole tools or members thereof, which will be described later, it is possible to extend the sealing holding time even under high temperature conditions.
- the resin molded body in the present embodiment preferably has a tensile strength of 80 MPa or more, and preferably 90 MPa or more, from the viewpoint of withstanding high pressure in the well and retaining sealing in the application of a downhole tool or a member thereof described later. and more preferably 100 MPa or more.
- the tensile strength is preferably 400 MPa or less, more preferably 370 MPa or less, and even more preferably 350 MPa or less.
- the tensile strength of the resin molding is measured by using a type 1A tensile test piece and pulling it at a speed of 50 mm/min under an environment of 23° C. in accordance with ISO527.
- the resin composition according to the first embodiment of the present invention comprises 50 parts by mass or more and 97 parts by mass or less of PGA, 3 parts by mass or more and 50 parts by mass or less of PBT, and the total amount of PGA and PBT of 100 parts by mass 2 parts by mass or more and 15 parts by mass or less of cyc-CDI.
- a downhole tool or a member thereof made of a resin composition having this composition can further suppress water intrusion in an 80° C. underwater environment compared to a composition that does not contain PBT. Therefore, the resin composition makes it possible to suppress reduction in the thickness of downhole tools or members thereof in high-temperature wellbore.
- the content of cyc-CDI is 4 parts by mass or more with respect to the total amount of 100 parts by mass of PGA and PBT. good too.
- This configuration is much more effective from the viewpoint of reducing the rate of thickness reduction in water at 80° C. of the resin molded article compared to a composition that does not contain PBT.
- a downhole tool and a downhole tool member according to an embodiment of the present invention include a resin molded body formed by molding using the resin composition according to the embodiment of the present invention as a raw material.
- a part of the downhole tool or its member according to the embodiment of the present invention may contain a resin molded body, or may be entirely formed of a resin molded body.
- the part of the resin molded body may be an integral part in the downhaul tool or its member. However, it may be another part that is separately combined.
- a downhole tool means a tool itself for forming or collecting downholes for recovering hydrocarbon resources such as oil and gas in the ground.
- downhole tools include plugs, washpipes, cement retainers, perforation guns, ball sealers, filler plugs and packers.
- the downhole tool member means a member that constitutes the coupling portion in the downhole tool.
- the joint part is a part that joins a plurality of parts that constitute the downhole tool to form the downhole tool, or is directly or indirectly coupled to the downhole to realize the usage form in the downhole. means part.
- plugs include plugs as downhole tools and plugs as downhole tool members.
- a plug according to an embodiment of the present invention is a plug for temporarily obstructing the flow of fluid in a well, and is the above-described downhole tool or its member.
- the plug can be both a downhole tool plug and a downhole tool member.
- plugs as downhole tools include flack plugs and bridge plugs.
- plugs as downhole tool members include balls, darts, discs, screws and packers.
- Plug (First aspect of the plug)
- a plug that is used by closing an opening that communicates the inside and outside of a tubular member inserted into a well provided on the peripheral surface of the tubular member will be described.
- Such plugs can be, for example, balls, darts, discs, screws and packers applied to downhole tools.
- downhole tools to which plugs of the first aspect are applied include wash pipes for cleaning wells and stimulating formations before fracturing.
- FIG. 1 is a schematic cross-sectional view of a downhole tool to which a plug according to the first aspect of the invention is applied.
- a downhole tool 1 shown in FIG. 1 is inserted into a well, and includes a tubular main body 14 as a tubular member.
- the downhole tool 1 has a first opening 16 at the beginning and a second opening 17 at the end, and further has one or more third openings 18 between the beginning and the end.
- "20" represents a well wall.
- the third opening 18 is provided on the peripheral surface of the tubular main body 14 and is an opening that allows communication between the inside and the outside of the tubular main body 14 .
- a screw-like plug 11 is inserted into the third opening 18 so as to block the third opening 18, and the plug 11 is engaged with the third opening.
- the third opening 18 of the tubular body 14 is closed by the plug 11 .
- the “beginning end” of the downhole tool refers to the end located on the entrance side of the well while the downhole tool is set in the well, and when inserting the downhole tool into the well, Refers to the end that is inserted last.
- “Terminal” is the end on the opposite side from the start end, and in a wellbore, it refers to the end located on the far side when the wellbore is viewed from the entrance, and when the downhole tool is inserted into the wellbore refers to the end that is inserted first into the
- the plug 11 is a screw-like plug that closes an opening provided on the peripheral surface of the tubular member that allows communication between the inside and the outside of the tubular member.
- the plug 11 is configured by the resin molding according to this embodiment.
- the plug 11 By inserting the plug 11 into the third opening 18 of the tubular body 14, the flow of fluid from the inside of the tubular body 14 to the outside through the third opening 18 is blocked.
- the third opening 18 is released by disassembling the plug 11 made of a resin molded body, and as a result, the plug 11 is directed from the inside to the outside of the cylindrical main body 14 through the third opening 18 . Fluid flow or fluid flow from the outside to the inside of the tubular body 14 will occur.
- the size of the plug 11 may vary depending on the thickness of the tubular body 14 to which it is applied.
- the shortest distance L1 between the first surface 121 of the plug 11 and the second surface 122 of the plug 11 exposed inside the tubular body 14 may be 6 mm or more and 65 mm or less.
- FIG. 2 is an enlarged schematic view of a part of a cross section of a downhole tool to which Modified Example 1 of the first aspect of the plug according to the embodiment of the present invention is applied.
- the downhole tool 2 according to Modification 1 has a third opening 28 of a cylindrical main body 24 closed by a threaded plug 21 .
- the plug 21 according to Modification 1 is, like the plug 11 described above, a plug that closes an opening that communicates the inside and outside of the tubular member provided on the peripheral surface of the tubular member.
- the plug 21 according to Modification 1 is composed of a body portion 22 formed of the resin molded body according to the present embodiment and an annular molded body 23 formed of a non-degradable material. , the plug 11 is different.
- the annular molded body 23 in Modification 1 is an annular member that covers the periphery of the body portion 22 and has threads on the outer peripheral surface.
- the body portion 22 is arranged inside the ring of the annular molded body 23 .
- the annular molded body 23 in Modification 1 is made of a non-degradable material such as SUS303 and SUS304.
- non-degradable material refers to a material that does not readily lose weight or thickness in the wellbore environment.
- the annular shaped body 23 is preferably formed of a material that does not substantially lose weight or thickness for 30 days or more in a wellbore.
- the plug 21 is inserted into the third opening 28 of the tubular main body 24, so that the flow of fluid from the inside of the tubular main body 24 to the outside through the third opening 28 is prevented. flow is obstructed. Then, by disassembling the main body 22 of the plug 21 made of a resin molded body, the third opening 28 is released. A fluid flow from the inside to the outside of the tubular body 24 or from the outside to the inside of the tubular body 24 will occur through the inside of the ring of the body 23 .
- the size of the body portion 22 may be set as appropriate by those skilled in the art in the same manner as the size of the plug 11 .
- FIG. 3 is a schematic diagram showing an enlarged part of a cross section of a downhole tool to which modification 2 of the first aspect of the plug according to the embodiment of the present invention is applied.
- a cylindrical main body 34 provided in the downhole tool 3 in FIG. The plug 31 is engaged inside the tubular body 34 .
- the plug 31, which is the modification 2 of the first aspect, is applied to a cylindrical member having an opening on its peripheral surface for communicating the inside and the outside, like the plug 11 of the first aspect described above. However, it differs from the plug 11 in that it is not inserted into the opening.
- the plug 31 of Modification 2 engages with the tubular member inside the peripheral surface of the tubular member so as to close the opening.
- the third opening 38 is closed from the inside by the plug 31 engaging the inside of the tubular body 34 . This prevents the flow of fluid from the inside of the tubular body 34 to the outside through the third opening 38 .
- the third opening 38 is exposed, and the fluid flowing from the inside to the outside of the cylindrical main body 34 through the third opening 38 is disassembled. or flow of fluid from the outside of the tubular body 34 to the inside.
- a second aspect of the plug according to this embodiment includes a downhole plug (downhole tool) such as a frac plug or bridge plug that is inserted into a wellbore.
- the resin molding according to the present embodiment is used as downhole tool members such as mandrels, load rings, cones, sockets, and bottoms, but is not limited to this.
- a downhole plug, which is a second aspect of the plug according to the present embodiment will be described below with reference to FIG.
- FIG. 4 is a cross-sectional schematic diagram of a downhole plug when in place in a wellbore, in accordance with an embodiment of the present invention; Note that FIG. 4 shows only one of the cross sections symmetrical with respect to the axis of the downhole plug.
- the downhole plug 5 shown in FIG. 4 includes a mandrel 51 corresponding to a cylindrical member, a ball 53, a center element 52 attached around the outer peripheral surface of the mandrel 51, a socket 54, cones 55a and 55b, and a slip 56a. and 56b, equalizer rings 57a and 57b, load ring 58, and bottom 59.
- the downhole plug 5 has a cylindrical shape as a whole.
- the mandrel 51 functions as a central shaft that supports other members (hereinafter referred to as side parts) arranged on the outer periphery of the mandrel 51 and as a receiver for the balls 53 .
- the center element 52 is an annular rubber member that fills the gap between the mandrel 51 and the well wall 20 in the downhole plug 5 to seal the well, and is deformed by a load.
- the socket 54, the cone 55, the slip 56, the equalizer ring 57, and the load ring 58 directly or indirectly apply the load applied from the setting tool to the center element 52 when the downhole plug 5 is operated in the well. It is an element for transmission.
- the load ring 58 is a pressing jig that transmits the load applied from the setting tool to other side parts.
- the cone 55 has the function of promoting the diameter expansion of the slip 56 in the circumferential direction and compressing the center element 52 .
- the socket 54 has a function of preventing the center element 52 from flowing out to the far side when the well is viewed from the entrance.
- the bottom 59 prevents the downhole plug 5 from colliding with the well wall 20 and operating while the downhole plug 5 is being transported in the well, and also fixes other side parts during setting. have a function.
- the plugs described above are plugs that temporarily block the flow of fluids in a wellbore and can be used in wellbore treatment.
- the wellbore is preferably a cased well with a casing.
- the well treatment is performed by temporarily blocking the flow path of the fluid in one or more regions of at least one of the well and the downhole tool using a plug, and decomposing the resin molding of the plug. Including removing the stop and altering the fluid flow path in the region.
- the area where the plug temporarily blocks the flow path of the fluid is the downhole tool. corresponds to the downhole tool.
- the flow path of the fluid is a third opening provided on the peripheral surface of the cylindrical member of the downhole tool, which communicates the inside and the outside.
- the fluid flow is the flow of fluid from the inside of the tubular member, ie, the downhole tool, to the outside through the opening, or the flow of fluid from the outside of the downhole tool to the inside through the opening.
- the fluid channel temporarily blocked by the plug is the well, and the fluid channel temporarily The area that fills in is part of the well.
- Another aspect of well treatment is to install a plug in the well to impede the flow of fluid in the well, and to restore the flow of fluid by decomposing the resin molding that constitutes the plug.
- the resin compact forming the plug is decomposed by the water contained in the fluid present in the well, so that the well is unblocked and the fluid flow is restored.
- the downhole tool shown in FIG. As a more specific method of well treatment using the plug of the first aspect, the downhole tool shown in FIG.
- the well processing method using the downhole tool shown in FIG. This is a well processing method for temporarily closing the opening 18 .
- Well cleaning is performed in the following procedure before fracturing for the purpose of increasing the efficiency of recovering hydrocarbon resources.
- the downhole tool 1 is introduced to an arbitrary position in the well using a fluid or the like.
- a fluid such as water is injected into the tubular body 14 from the ground through the first opening 16 and jetted into the well through the second opening 17 to wash the well.
- Liquids such as water, oil, and emulsions are generally used as fluids, and in some cases, these fluids contain salts from several ppm to several tens of percent.
- the third opening 18 is closed by the plug 11 , the fluid injected through the first opening 16 is not ejected from the third opening 18 .
- the fluid injected into the well from the second opening 17 passes through the gap between the outside of the downhole tool 1 and the well wall 20, and is accompanied by sand, scale, etc. deposited on the inner wall of the well, and is discharged on the ground. is recovered by
- the plug 11 since the third opening 18 is blocked by the plug 11, the fluid accompanied by sand, scale, etc. after cleaning the wellbore flows through the third opening 18 into the downhole tool. can be prevented from entering. Therefore, it is possible to prevent a decrease in the efficiency of the cleaning work. Thus, it is important to maintain the plug 11 so as not to unblock the third opening during the cleaning operation.
- the inside and outside of the cylindrical body 14 can be communicated through the third opening 18 . This enables circulation of the fluid inside and outside the downhole tool 1 via the third opening 18 .
- the procedure for stimulating the stratum is as follows. First, a stimulating fluid for stimulating the stratum is injected into the tubular body 14 from the ground through the first opening 16 . The injected stimulation fluid is injected through the third opening 18 into the wellbore wall 20 to stimulate the formation. This stimulation increases the amount of hydrocarbon resources recovered from the formation, which can contribute to an increase in production efficiency.
- the production fluid containing hydrocarbon resources that has flowed out of the formation into the well can be recovered to the surface via the third opening 18 and the first opening 16.
- the plug it is possible to maintain the sealing function in a plurality of areas of the downhole tool in a well in a high-temperature environment for a desired period of time, and after the desired period of time has passed, the plug can be It is possible to obtain a plug that decomposes favorably even in As a result, it is possible to more reliably seal the sealant for a desired period of time, and further reduce the risk of clogging at the sealant position.
- FIG. 4 is a cross-sectional schematic diagram of a downhole plug when in place in a wellbore, in accordance with an embodiment of the present invention
- FIG. 5 is a schematic illustration of a cross-section of a downhole plug while plugging a well according to an embodiment of the present invention
- 4 and 5 show only one of the cross sections symmetrical with respect to the axis of the downhole plug.
- the downhole plug 5 is introduced from the ground to an arbitrary position inside the well using a fluid or the like. Thereafter, the setting tool is activated to deform the center element 52 as shown in FIG.
- the starting end of the mandrel 51 of the downhole plug 5 is closed to complete the sealing.
- a sealing method for example, as shown in FIG. 5, a ball 53 supplied toward the starting end of the downhole plug 5 is arranged at the starting end of the mandrel 51 to close one end of the mandrel 51. is mentioned.
- the downhole plug 5 can be used as a boundary to separate the space on the entrance side and the depth side of the well.
- the ball 53 may be placed at the beginning of the mandrel 51 by allowing it to flow in with the fluid from the ground.
- hydraulic fracturing Such a method of enlarging fractures by injecting fluid is called hydraulic fracturing.
- the downhole plug 5 After the fracturing is completed, the downhole plug 5 is brought into contact with a fluid containing water to decompose the resin molding that constitutes part or all of the downhole plug 5 . As a result, the downhole plug 5 loses its original shape and the well is unblocked.
- the plug according to the present embodiment it is possible to maintain the sealing function in a plurality of regions of a well in a high temperature environment for a desired period of time, and after the desired period of time has passed, it is suitable even in fluids or water with a low salt concentration. It is possible to decompose. As a result, sealing can be reliably performed for a desired period of time, and the risk of clogging at the sealing position can be reduced.
- a downhole tool or a member thereof according to a third embodiment of the present invention includes a resin molded body formed by molding using the resin composition according to the first embodiment or second embodiment described above as a raw material.
- a plug according to a fourth embodiment of the present invention is a plug for temporarily obstructing the flow of fluid in a well, and is a downhole tool or a member thereof according to the third embodiment.
- the downhole tool or its member or plug in the embodiment of the present invention includes a resin molded body made of the above-mentioned resin composition as a main part, the thickness of the downhole tool or its member in a high-temperature wellbore is reduced. It is possible to suppress the decrease.
- the plug according to the fifth embodiment of the present invention may be a ball, dart, disk, screw or packer in the fourth embodiment described above.
- a plug according to a sixth embodiment of the present invention is used to close an opening provided in the peripheral surface of a tubular member in the fourth embodiment described above and communicating between the inside and outside of the tubular member,
- the portion of the resin molded body has a first surface exposed to the outside of the tubular member during use and a second surface exposed to the inside of the tubular member during use. and the second surface may be 6 mm or more and 65 mm or less.
- a plug according to a seventh embodiment of the present invention is a plug according to any one of the fourth to sixth embodiments described above, wherein the portion of the resin molded body is replaced by another molded body made of a non-degradable material. At least a portion may be covered.
- a plug according to an eighth embodiment of the present invention is, in the above-described seventh embodiment, wherein the another molded body is an annular molded body having a threaded outer peripheral surface, and the resin molded body The part may be arranged inside the ring of said annular shaped body.
- the plug of the ninth embodiment of the present invention may be a flack plug or a bridge plug in the fourth embodiment described above.
- a downhole tool of a tenth embodiment of the present invention may comprise a tubular member and the plug of any one of the fourth to eighth embodiments described above, the tubular member comprising:
- the peripheral surface of the tubular member may have an opening communicating between the inside and the outside of the tubular member, and the plug may be engaged with the tubular member so as to block the opening.
- any of the above downhole tools or members thereof includes a resin molded body made of the above-mentioned resin composition as a main part. Therefore, it is much more effective from the viewpoint of suppressing reduction in thickness when used in high-temperature wells in each of the forms and applications specified above.
- a well processing method uses the plug according to any one of the fourth to ninth embodiments described above to perform at least one of a well and a downhole tool. Temporarily blocking one or more regions, and decomposing the resin molded body portion of the plug to eliminate the temporary blocking by the plug and change the flow path of the fluid in the region to do.
- the plug according to any one of the fourth to ninth embodiments described above is installed in the well, and the fluid in the well is and decomposing the resin molding to restore the flow of the fluid.
- the well processing method according to the thirteenth embodiment of the present invention includes (1) a first opening at one end, a second opening at the other end, and a second opening between the one end and the other end.
- a downhole tool having three openings, the third opening being sealed by a plug as a downhole tool member according to any one of the fourth to eighth embodiments described above.
- (2) pressurizing a fluid from the ground into the downhole tool through the first opening, and jetting the fluid into the wellbore from the second opening to clean the wellbore and (3) disassembling the resin molded body portion of the plug after cleaning to enable fluid flow inside and outside the downhole tool through the third opening. can contain.
- a downhole tool or its member containing a resin molded body made of the resin composition described above is used. Therefore, it is possible to reduce the thickness reduction of the downhole tool or its members in hot wellbore in each of the applications identified above.
- Example 1 Polyglycolic acid (PGA, "Kuredux 100R90” manufactured by Kureha Co., Ltd., weight average molecular weight (Mw): 210,000), polybutylene terephthalate (PBT, "Novaduran (registered trademark) 5010R5" manufactured by Mitsubishi Engineering-Plastics Corporation), polyethylene Terephthalate (PET, "RY518X” manufactured by Toyobo Co., Ltd.) and cyclic carbodiimide (cyc-CDI, "Carbosista (registered trademark)” manufactured by Teijin Limited, grade “TCC-NP”) were prepared.
- PGA Polyglycolic acid
- PBT polybutylene terephthalate
- PET polyethylene Terephthalate
- cyc-CDI cyclic carbodiimide
- the resin composition 1 is put into an injection molding machine in which the temperature of the screw part is set to 210 to 255 ° C., injection molding is performed at a mold temperature of 100 ° C., and the resin is molded into a cube with a side width of 12.5 mm. Body 1A was produced. Further, under the same conditions, a resin molding 1B, which is a dumbbell-shaped tensile test piece (1A test piece), was produced.
- Example 2 A pellet-shaped resin composition 2 was produced in the same manner as in Example 1 except that the amount of cyc-CDI was changed to 3 parts by mass, and a cubic resin molding 2A and a dumbbell-shaped resin molding 2B were produced. .
- pellet-shaped resin composition 3 was produced in the same manner as in Example 1 except that the amount of cyc-CDI was changed to 10 parts by mass, and a cubic resin molded body 3A and a dumbbell-shaped resin molded body 3B were produced. made.
- Example 4 A pellet-shaped resin composition 4 was produced in the same manner as in Example 1, except that the amount of PGA was changed to 55 parts by mass and the amount of PBT was changed to 45 parts by mass. A resin molding 4B was produced.
- Example 2 In the same manner as in Example 1, except that the amount of PGA was changed to 95 parts by mass and the amount of PBT was changed to 5 parts by mass, a pellet-shaped resin composition 5 was produced, and a cubic resin molded body 5A and a dumbbell A mold resin molding 5B was produced.
- Example 2 Furthermore, in the same manner as in Example 1, except that the amount of PGA was changed to 85 parts by mass and the amount of PBT was changed to 15 parts by mass, a pellet-shaped resin composition 6 was produced, and a cubic resin molded body 6A and a dumbbell A mold resin molding 6B was produced.
- Example 1 A pellet-shaped resin composition C1 was produced in the same manner as in Example 1 except that the amount of cyc-CDI was changed to 1 part by mass, and a cubic resin molded product C1A and a dumbbell-shaped resin molded product C1B were produced. .
- a pellet-shaped resin composition C2 was prepared in the same manner as in Example 1 except that polyethylene terephthalate (PET, "RY518X” manufactured by Toyobo Co., Ltd.) was used instead of PBT, and a cubic resin molded body C2A and a dumbbell-shaped A resin molding C2B was produced.
- PET polyethylene terephthalate
- RY518X manufactured by Toyobo Co., Ltd.
- a pellet-shaped resin composition C3 was produced in the same manner as in Example 1 except that polylactic acid (PLA, “4032D” manufactured by Natureworks) was used instead of PBT, and a cubic resin molded product C3A and a dumbbell-shaped resin composition C3 were prepared.
- a resin molding C3B was produced.
- a pellet-shaped resin composition C4 was prepared in the same manner as in Example 1 except that 100 parts by mass of PGA was used instead of 70 parts by mass of PGA, 30 parts by mass of PBT and 5 parts by mass of cyc-CDI.
- a cubic resin molded body C4A and a dumbbell-shaped resin molded body C4B were produced.
- Pellets were prepared in the same manner as in Example 1 except that 70 parts by mass of PGA, 30 parts by mass of PBT and 5 parts by mass of cyc-CDI were replaced with 100 parts by mass of PGA and 3 parts by mass of cyc-CDI.
- a resin composition C5 was prepared, and a cubic resin molded article C5A and a dumbbell-shaped resin molded article C5B were prepared.
- Example 2 In the same manner as in Example 1, except that 100 parts by mass of PGA and 20 parts by mass of cyc-CDI were used instead of 70 parts by mass of PGA, 30 parts by mass of PBT and 5 parts by mass of cyc-CDI.
- a cubic resin molded product C6A and a dumbbell-shaped resin molded product C6B were prepared.
- Example 7 A pellet-shaped resin composition C7 was produced in the same manner as in Example 1 except that cyc-CDI was not used, and a cubic resin molded product C7A and a dumbbell-shaped resin molded product C7B were produced.
- a graph was created by plotting the acquired data with time (hr) on the horizontal axis and the amount of thickness reduction on the vertical axis, and the slope of the straight line calculated by the least squares method was calculated.
- the slope of the obtained straight line is the thickness reduction rate ( ⁇ m/hr).
- the amount of reduction in thickness is the average of the differences in length, width and height of the resin molding A before and after immersion. Plots with a thickness reduction amount of 0.01 mm or less were excluded from the calculation because they could include length measurement errors.
- compositions and evaluation results of Resin Compositions 1 to 6 are shown in Table 1 below.
- compositions and evaluation results of resin compositions C1 to C7 are shown in Table 1 below.
- R 80 represents the thickness reduction rate ( ⁇ m/hr) in water at 80° C.
- S represents the stress (MPa) at the maximum tensile point.
- FIG. 6 shows the observation positions of the microscopic structure of the resin molding.
- a melt-kneaded resin composition was injected from a gate G in the injection direction Di to prepare a rod-shaped resin molding.
- the resin molded body was cut at a position of 40 mm from the tip in the injection direction Di of the resin molded body to form a cross section So perpendicular to the injection direction Di.
- the cross section So was observed with a scanning electron microscope (SEM).
- FIG. 7 shows a SEM photograph of a cross section of the resin molding A having a mass ratio of PGA:PBT of 90:10.
- the PBT phase is dispersed in the PGA phase.
- Most of the PBT phases have a size of 500 nm or less, and even the largest ones are 1 ⁇ m or less.
- PBT is well dispersed in PGA.
- Fig. 8 shows an SEM photograph of the cross section of resin molding B (Comparative Example 7) having a mass ratio of PGA:PBT of 70:30.
- the PBT phase is dispersed in the PGA phase, but the size of the PBT phase is larger than that of the resin composition A, and larger particles of 2 to 5 ⁇ m are increased.
- the size of the PBT phase tends to be larger at the center of the cross section and smaller at the edges.
- the dispersibility of the PBT phase is lowered. This is presumed to be due to poor cutting of the PBT phase during the molding process.
- FIG. 9 shows an SEM photograph of the cross section of the resin molding C (Example 1) having a mass ratio of PGA:PBT:cyc-CDI of 70:30:5.
- resin composition C poor dispersion of the PBT phase in the PGA phase is more pronounced.
- a belt-like distribution of the PBT phase is observed, and the belt-like PTB phase is oriented in the injection direction. This is presumed to be due to poor cleavage of the PBT phase during the molding process, and further presumed to be due to the fact that the reaction with cyc-CDI further elongated the PBT, thereby aggravating the above-mentioned poor cleavage.
- Fig. 10 shows an SEM photograph of the cross section of the resin molding D (Comparative Example 7) having a mass ratio of PGA:PET of 70:30.
- the PET phase is dispersed in the PGA phase.
- Most of the PET phases have a size of 1 to 5 ⁇ m.
- PET is well dispersed in PGA.
- FIG. 11 shows an SEM photograph of the cross section of the resin molding E (Comparative Example 2) having a mass ratio of PGA:PET:cyc-CDI of 70:30:5.
- resin composition E the PET phase is finely dispersed in the PGA phase.
- the size of most of the PET phases is 2 ⁇ m or less, which is smaller than that of resin composition D. Also, the shape of many PET phases is nearly circular.
- the first reason is that the PBT phase exhibits a barrier function against the intrusion of water into the resin molding. That is, the PBT phase in the resin composition is initially finely dispersed in the PGA phase, and in the process of molding, the PBT are bonded to each other via the cyclic carbodiimide compound, resulting in longer molecular chains of PBT. As a result, the melt viscosity of PBT becomes sufficiently high relative to that of PGA, and the melt miscibility between PGA and PBT is reduced. Then, the PBT phase becomes larger and is distributed in the PGA phase in a streak-like or network-like manner.
- the PBT phase which is distributed more roughly than at the beginning of kneading, prevents water from entering the resin molded body, suppresses contact of water with the PGA phase, and As a result, it is considered that the decomposition retarding effect for water at 80°C is exhibited.
- the second reason is that unreacted cyc-CDI reacts with water that enters the resin molding. That is, it is thought that the smaller the amount of PBT, the more unreacted cyc-CDI remains. It is thought that this unreacted cyc-CDI consumes the water that has entered the resin molding, thereby suppressing the contact between PGA and water and slowing down the thickness reduction.
- Example 5 This is inferred from, for example, a comparison between Example 5 and Example 6, or a comparison between Comparative Example 4 and Comparative Example 5 or Comparative Example 6. That is, in 5 parts by mass of PBT (Example 5), carbodiimide consumed in the reaction with COOH is less than in 15 parts by mass of PBT (Example 6), so unreacted carbodiimide remains more. It is believed that such a difference causes the difference in thickness reduction rate between Example 5 and Example 6.
- the thickness reduction rate R80 of both Examples 5 and 6 is smaller than that of Comparative Example 4, which does not contain PBT and cyc-CDI. Therefore, until the amount of PBT is at least 15 parts by mass (15% by mass with respect to the total amount of the resin components), the effect of further retarding the thickness reduction rate R 80 is that the PBT phase is dispersed in the PGA phase in the resin molded body. It is considered that the presence of a large amount of unreacted cyc-CDI in the resin molding has a greater effect than the above.
- the distance between the PBT phases in the resin molding is minimized when the PBT content is in the range of 10 to 15%.
- the distance between the PBT phases in the resin molded body A is shorter than that in the resin molded body B.
- the thickness reduction rate R 80 of the resin molding containing 100 parts by mass of PGA and 5 parts by mass of cyc-CDI is between Comparative Example 5 and Comparative Example 6 (actually over 40 ⁇ m/hr).
- the amount of PBT is about 15% by mass of the resin component.
- the rate of decrease R80 is highest, but thereafter it is believed that the R80 decreases as the amount of PBT increases. Therefore, when the amount of PBT is up to about 15% by mass in the resin component, the PBT phases do not aggregate and are finely dispersed even when cyc-CDI is contained.
- Comparative Example 7 Comparative Example 1, and Examples 1 to 3, the R 80 of the resin molded body in which PGA/PBT is 70/30 by mass parts, the amount of cyc-CDI is up to 1 part by mass ( Comparative Example 7 and Comparative Example 1) are higher than that of the resin molded product of PGA and cyc-CDI, but when the amount of cyc-CDI is more than 3 parts by mass (Examples 1 to 3), PGA and cyc - Lower than that of resin moldings with CDI.
- R 80 of Comparative Example 2 (PGA/PET/cyc-CDI is 70/30/5) is 61.7 ⁇ m/hr, and Comparative Example 3 (PGA/PLA/cyc-CDI is 70/30/5)
- the R 80 of PBT is 66.0 ⁇ m /hr . This is considered to be an effect peculiar to the resin molding containing
- the present invention can be used in various technical fields using resin materials that can be decomposed by hydrolysis in water while being able to suppress decomposition in water at high temperatures, and in such situations.
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Abstract
Description
本発明の一実施形態に係る樹脂組成物は、ポリグリコール酸と、ポリブチレンテレフタレートと、環状カルボジイミド化合物とを含む。
本実施形態におけるポリグリコール酸は、-(-O-CH2-CO-)-で表される繰り返し単位を含有するポリマーである。ポリグリコール酸は、グリコール酸の単独重合体であることが好ましいが、グリコール酸と他のモノマー成分との共重合体でもよい。
本発明の実施形態におけるポリブチレンテレフタレートは、テレフタル酸単位及び1,4-ブタンジオール単位がエステル結合した構造を有するポリエステルである。ポリブチレンテレフタレートは、テレフタル酸と1,4-ブタンジオールとを重縮合させたポリブチレンテレフタレートの単独重合体(ホモポリマー)が好ましいが、コポリマーであってもよいし、それらの混合物であってもよい。
本実施形態におけるポリグリコール酸樹脂組成物に含まれる環状カルボジイミド化合物は、カルボジイミド基の第一窒素と第二窒素とが結合基により結合されている環状構造を有する化合物である。環状カルボジイミド化合物は、たとえば下記式(I)で表すことができる。
本発明の実施形態の樹脂組成物におけるPGAの含有量は、50質量部以上97質量部以下である。PGAの含有量が50質量部以上であることは、樹脂成形体にPGA由来の速やかな分解特性を十分に付与する観点から好ましく、当該分解特性の向上の観点から、55質量部以上であることがより好ましく、60質量部以上であることがさらに好ましい。また、PGAの含有量が97質量部以下であることは、樹脂成形体の80℃の水中における厚み減少速度を十分に抑制する観点から好ましく、当該厚み減少速度の抑制の観点から、90質量部以下であることがより好ましく、80質量部以下であることがさらに好ましい。
本発明の実施形態の樹脂組成物には、本発明の実施形態の効果が得られる範囲において、熱安定剤、酸化防止剤、耐衝撃改質剤、架橋剤、有機フィラー、無機フィラー、および着色剤等の他の添加剤が含まれていてもよい。
本発明の実施形態の樹脂組成物の形態は限定されない。樹脂組成物は、粉末状の原料の混合物であってもよいし、ペレットなどの、これらの原料の溶融混練物であってもよい。たとえば、樹脂組成物において、PGAの末端が環状カルボジイミド化合物によってキャッピングされていてもよく、PBTの末端が環状カルボジイミド化合物によってキャッピングされていてもよい。ここで、「キャッピングされている構造」とは、PGAまたはPBTの末端のカルボキシル基と環状カルボジイミド化合物とが反応することによって得られる構造を意味する。PGAまたはPBTの末端の一部が、環状カルボジイミド化合物によってキャッピングされていてもよい。PGAまたはPBTの末端の一部が、環状カルボジイミド化合物によってキャッピングされている場合では、本実施形態の樹脂組成物は、PGA、PBTおよび環状カルボジイミド化合物に加えて、例えばPGAまたはPBTの末端に環状カルボジイミド化合物が反応、結合することで構成された、環状カルボジイミド化合物の誘導体をさらに含んでいてもよい。
(樹脂成形体の製造方法)
本発明の実施形態の樹脂組成物を原料とする成形によって樹脂成形体が形成される。当該樹脂成形体は、PGA、PBTおよびcyc-CDIを混合し、該混合物の固化押出成形または射出成形によって製造することができる。該混合物は、PGA、PBTおよびcyc-CDIを溶融混錬し、ペレット化したものであり得る。溶融混錬する場合、PGAの熱分解抑制の観点から、温度は、220~280℃であることが好ましく、230~260℃であることがより好ましい。
樹脂成形体は、本発明の実施形態の樹脂組成物から形成されるため、塩濃度の低い流体または水においても好適に分解する。当該樹脂成形体を水に浸漬すると、樹脂成形体の表層部におけるPGAは、加水分解によって分子量が低下する。この結果、樹脂成形体の表層部が脆くなる。分子量が低下したPGAは水を透過するので、樹脂成形体の表層部から中心部にかけて徐々にPGAが加水分解される。こうして、樹脂成形体の脆化が進行する。分子量が低下したPGAがさらなる加水分解によってさらに低分子量化すると、加水分解生成物として生成したオリゴマーまたはグリコール酸が水に溶出する。その結果、樹脂成形体は形状を失う。このようにして、樹脂成形体は最終的に分解される。樹脂成形体を後述するダウンホールツールまたはその部材に使用する場合では、樹脂成形体の分解により、樹脂成形体による目止めが解除される。
本実施形態における樹脂成形体は、後述のダウンホールツールまたはその部材の用途において、坑井内の高い圧力に耐えて目止めを保持する観点から、引張強度が80MPa以上であることが好ましく、90MPa以上であることがより好ましく、100MPa以上であることがさらに好ましい。また、成形加工を容易にする観点から、引張強度は400MPa以下であることが好ましく、370MPa以下であることがより好ましく、350MPa以下であることがさらに好ましい。ここで、樹脂成形体の引張強度は、タイプ1Aの引張試験片を用いて、ISO527に準拠して23℃の環境下で50mm/minの速度で引っ張ることで測定される。
本発明の第一の実施形態に係る樹脂組成物は、50質量部以上97質量部以下のPGAと、3質量部以上50質量部以下のPBTと、PGAおよびPBTの総量100質量部に対して2質量部以上15質量部以下のcyc-CDIとを含む。当該組成を有する樹脂組成物を材料としたダウンホールツールまたはその部材では、80℃水中の環境下において、PBTを含まない組成に比べて水の侵入をより抑制することが可能である。よって、当該樹脂組成物は、高温の坑井内におけるダウンホールツールまたはその部材の厚みの減少を抑制することを可能とする。
本発明の実施形態のダウンホールツールおよびダウンホールツール部材は、上記の本発明の実施形態の樹脂組成物を原料とする成形によって形成された樹脂成形体を含む。本発明の実施形態のダウンホールツールまたはその部材は、その一部が樹脂成形体を含んでいてもよいし、全部が樹脂成形体で形成されていてもよい。本発明の実施形態のダウンホールツールまたはその部材は、その一部が樹脂成形体を含む場合は、樹脂成形体の部分は、そのダウンホールツールまたはその部材において一体的な部分であってもよいし、別途組み合わされる別の部品であってもよい。
本発明の実施形態のプラグは、坑井内の流体の流通を一時的に妨げるためのプラグであって上記のダウンホールツールまたはその部材である。プラグは、前述したように、ダウンホールツールであるプラグとダウンホールツール部材であるプラグとの両方があり得る。ダウンホールツールとしてのプラグの例には、フラックプラグおよびブリッジプラグが含まれる。ダウンホールツール部材としてのプラグの例には、ボール、ダート、ディスク、ネジおよびパッカーが含まれる。
(プラグの第1の態様)
本発明の実施形態に係るプラグの第1の態様として、坑井に挿入された筒状部材の周面部に設けた該筒状部材の内外を連通させる開口部を塞いで使用するプラグについて説明する。このようなプラグは、例えば、ダウンホールツールに適用されるボール、ダート、ディスク、ネジおよびパッカーであり得る。また、これら第1の態様のプラグが適用されるダウンホールツールの例として、フラクチャリング前に坑井を洗浄したり地層を刺激したりするためのウォッシュパイプを挙げることができる。
本実施形態に係るプラグの第1の態様の変形例1について図2を用いて説明する。図2は、本発明の実施形態に係るプラグの第1の態様の変形例1を適用したダウンホールツールの断面の一部を拡大した模式図である。変形例1に係るダウンホールツール2は、上述のダウンホールツール1と同じく、筒状本体24の第3の開口部28が、ネジ状のプラグ21によって目止めされている。
本実施形態に係るプラグの第1の態様の変形例2について図3を用いて説明する。図3は、本発明の実施形態に係るプラグの第1の態様の変形例2を適用したダウンホールツールの断面の一部を拡大した模式図である。図3におけるダウンホールツール3が備える筒状本体34には、その周面に、筒状本体34の内外を連通させる第3の開口部38が設けられている。筒状本体34の内側には、プラグ31が係合している。
本実施形態に係るプラグの第2の態様として、坑井に挿入されるフラックプラグまたはブリッジプラグなどのダウンホールプラグ(ダウンホールツール)が挙げられる。本態様のダウンホールプラグでは、マンドレル、ロードリング、コーン、ソケット、およびボトム等のダウンホールツール部材として本実施形態に係る樹脂成形体が使用されているが、これに限定されるものではない。以下、本実施形態に係るプラグの第2の態様であるダウンホールプラグについて、図4を用いて説明する。図4は、本発明の実施形態に係る、坑井内の所定の位置にあるときの、ダウンホールプラグの断面の概略図である。なお、図4では、ダウンホールプラグの軸に対して対称な断面のうち一方のみを示している。
先に説明したプラグは、坑井内の流体の流通を一時的に妨げるプラグであり、坑井処理に用いることができる。本実施形態において、坑井はケーシングを有するcased wellであることが好ましい。
第1の態様のプラグを用いた坑井処理のより具体的な方法として、図1に示すダウンホールツールを用いて、坑井を洗浄する処理および地層を刺激する処理を説明する。図1に示すダウンホールツールを用いた坑井処理方法は、第1の態様のプラグであるネジ状のプラグ11が、ダウンホールツール1の筒状本体14の周面に設けられた第3の開口部18を一時的に目止めする場合の坑井処理方法である。
第2の態様のプラグを用いた坑井処理のより具体的な方法の一例として、図4および図5に示すダウンホールプラグを用いてフラクチャリング行う場合の方法を説明する。これは、第2の態様のプラグに対応するダウンホールプラグが坑井を一時的に目止めする場合の坑井処理方法である。図4は、本発明の実施形態に係る、坑井内の所定の位置にあるときの、ダウンホールプラグの断面の概略図である。図5は、本発明の実施形態に係る、坑井を目止めしているときの、ダウンホールプラグの断面の概略図である。なお、図4および図5は、ダウンホールプラグの軸に対して対称な断面のうち一方のみを示している。
本発明の第三の実施形態に係るダウンホールツールまたはその部材は、前述した第一の実施形態または第二の実施形態に係る樹脂組成物を原料とする成形によって形成された樹脂成形体を含む。また、本発明の第四の実施形態に係るプラグは、坑井内の流体の流通を一時的に妨げるためのプラグであって、上記の第三の実施形態に係るダウンホールツールまたはその部材である。本発明の実施形態におけるダウンホールツールまたはその部材あるいはプラグは、前述の樹脂組成物を材料とする樹脂成形体を要部に含むことから、高温の坑井内におけるダウンホールツールまたはその部材の厚みの減少を抑制することが可能である。
ポリグリコール酸(PGA、株式会社クレハ製「Kuredux 100R90」、重量平均分子量(Mw):21万)、ポリブチレンテレフタレート(PBT、三菱エンジニアリングプラスチックス株式会社製「ノバデュラン(登録商標) 5010R5」)、ポリエチレンテレフタレート(PET、東洋紡株式会社製「RY518X」)、および、環状カルボジイミド(cyc-CDI、帝人株式会社製「カルボジスタ(登録商標)」、グレード「TCC-NP」)を用意した。
cyc-CDIの量を3質量部に変更する以外は実施例1と同様にして、ペレット状の樹脂組成物2を作製し、立方体の樹脂成形体2Aおよびダンベル型の樹脂成形体2Bを作製した。
PGAの量を55質量部、PBTの量を45質量部にそれぞれ変更する以外は実施例1と同様にして、ペレット状の樹脂組成物4を作製し、立方体の樹脂成形体4Aおよびダンベル型の樹脂成形体4Bを作製した。
cyc-CDIの量を1質量部に変更する以外は実施例1と同様にして、ペレット状の樹脂組成物C1を作製し、立方体の樹脂成形体C1Aおよびダンベル型の樹脂成形体C1Bを作製した。
PBTに代えてポリエチレンテレフタレート(PET、東洋紡株式会社製「RY518X」)を用いる以外は実施例1と同様にして、ペレット状の樹脂組成物C2を作製し、立方体の樹脂成形体C2Aおよびダンベル型の樹脂成形体C2Bを作製した。
70質量部のPGA、30質量部のPBTおよび5質量部のcyc-CDIに代えて100質量部のPGAを用いる以外は実施例1と同様にして、ペレット状の樹脂組成物C4を作製し、立方体の樹脂成形体C4Aおよびダンベル型の樹脂成形体C4Bを作製した。
70質量部のPGA、30質量部のPBTおよび5質量部のcyc-CDIに代えて100質量部のPGAおよび3質量部のcyc-CDIを用いる以外は実施例1と同様にして、ペレット状の樹脂組成物C5を作製し、立方体の樹脂成形体C5Aおよびダンベル型の樹脂成形体C5Bを作製した。
cyc-CDIを用いない以外は実施例1と同様にして、ペレット状の樹脂組成物C7を作製し、立方体の樹脂成形体C7Aおよびダンベル型の樹脂成形体C7Bを作製した。
[1]分解性試験
立方体の樹脂成形体Aを用いて以下の(1)~(5)に従って分解性試験を実施し、厚み減少速度を算出した。
作製した樹脂成形体の引張最大点の応力を測定するため、引張試験を行った。引張試験は樹脂成形体B(タイプ1Aの引張試験片)を用いて、ISO527に準拠して23℃の環境下で50mm/minの速度で引っ張ることで測定した。
[樹脂成形体の準備]
樹脂成形体における樹脂の分散状態を観察する目的で、下記の樹脂成形体を、上記の条件で作製した。
PGA:PBTの質量比が90:10である樹脂成形体A
PGA:PBTの質量比が70:30である樹脂成形体B(比較例7)
PGA:PBT:cyc-CDIの質量比が70:30:5である樹脂成形体C(実施例1)
PGA:PETの質量比が70:30である樹脂成形体D
PGA:PET:cyc-CDIの質量比が70:30:5である樹脂成形体E(比較例2)
樹脂成形体の微視的構造の観察位置を図6に示す。まず、樹脂組成物の溶融混練物をゲートGから射出方向Diに射出して棒状の樹脂成形体を作製した。樹脂成形体の射出方向Diにおける先端から40mmの位置で樹脂成形体を切断し、射出方向Diに垂直な断面Soを形成した。断面Soを走査型電子顕微鏡(SEM)で観察した。
PGA:PBTの質量比が90:10である樹脂成形体Aの断面のSEM写真を図7に示す。樹脂成形体Aでは、PBT相がPGA相中に分散している。PBT相の大きさは、そのほとんどが500nm以下であり、大きいものでも1μm以下である。このように、樹脂成形体Aでは、PBTはPGA中に良好に分散している。
実施例1~6の樹脂成形体は、いずれも、PBTを含有しない樹脂成形体、例えばPGAのみからなる樹脂成形体C4(比較例4)に比べて、80℃の水中での厚み減少速度がより小さかった。これは、主に二つの理由によって樹脂成形体におけるPGA相への水の接触が抑制されたため、と考えられる。
5 ダウンホールプラグ
11、21、31 プラグ
14、24、34 筒状本体
16 第1の開口部
17 第2の開口部
18、28、38 第3の開口部
20 坑井壁
22 本体部
23 環状成形体
51 マンドレル
52 センターエレメント
53 ボール
54 ソケット
55、55a、55b コーン
56、56a、56b スリップ
57、57a、57b イコライザーリング
58 ロードリング
59 ボトム
121 第1の面
122 第2の面
Claims (13)
- 50質量部以上97質量部以下のポリグリコール酸と、
3質量部以上50質量部以下のポリブチレンテレフタレートと、
前記ポリグリコール酸および前記ポリブチレンテレフタレートの総量100質量部に対して2質量部以上15質量部以下の環状カルボジイミド化合物と、
を含む樹脂組成物。 - 前記環状カルボジイミド化合物の含有量が、前記ポリグリコール酸および前記ポリブチレンテレフタレートの総量100質量部に対して4質量部以上である、請求項1に記載の樹脂組成物。
- 請求項1に記載の樹脂組成物を原料とする成形によって形成された樹脂成形体を含む、ダウンホールツールまたはその部材。
- 坑井内の流体の流通を一時的に妨げるためのプラグであって請求項3に記載のダウンホールツールまたはその部材である、プラグ。
- ボール、ダート、ディスク、ネジまたはパッカーである、請求項4に記載のプラグ。
- 筒状部材の周面部に設けられた、前記筒状部材の内外を連通する開口部を塞ぐのに使用され、
前記樹脂成形体の部分は、使用時に前記筒状部材の外側に露出する第1の面と、使用時に前記筒状部材の内側に露出する第2の面とを有しており、
前記第1の面と前記第2の面との最短距離が6mm以上65mm以下である、請求項4に記載のプラグ。 - 前記樹脂成形体の部分は、非分解性材料からなる別の成形体によって少なくとも一部が覆われている、請求項4に記載のプラグ。
- 前記別の成形体は、外周面がネジ山で形成されている環状成形体であり、
前記樹脂成形体の部分は、前記環状成形体の環の内側に配置されている、請求項7に記載のプラグ。 - フラックプラグまたはブリッジプラグである、請求項4に記載のプラグ。
- 筒状部材と、請求項4~8のいずれか一項に記載のプラグとを備え、
前記筒状部材は、前記筒状部材の周面に前記筒状部材の内外を連通する開口部を有し、
前記プラグは、前記開口部を塞ぐように前記筒状部材に係合されている、ダウンホールツール。 - 請求項4~9のいずれか一項に記載のプラグを用いて、坑井およびダウンホールツールの少なくとも一方の一つ以上の領域を一時的に目止めすること、および、
前記プラグにおける前記樹脂成形体の部分を分解させることで前記プラグによる一時的な目止めを解消し、前記領域における流体の流路を変更すること、を含む、坑井処理方法。 - 請求項4~9のいずれか一項に記載のプラグを坑井に設置して、前記坑井内の流体の流れを妨げること、および、
前記樹脂成形体を分解させて前記流体の流れを回復すること、を含む、坑井処理方法。 - 一端に第1の開口部、他端に第2の開口部、前記一端と前記他端との間に第3の開口部を有し、前記第3の開口部が請求項4~8のいずれか一項に記載のダウンホールツール部材としてのプラグによって目止めされたダウンホールツールを坑井に導入すること、
前記第1の開口部を通じて地上から前記ダウンホールツールに流体を圧入して、前記第2の開口部から前記坑井内に前記流体を噴射させて前記坑井を洗浄すること、および、
洗浄後、前記プラグにおける前記樹脂成形体の部分を分解させて、前記第3の開口部を介した前記ダウンホールツール内外の流体の流通を可能とすること、を含む、坑井処理方法。
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