WO2022210240A1 - 成形物および加工品 - Google Patents
成形物および加工品 Download PDFInfo
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- WO2022210240A1 WO2022210240A1 PCT/JP2022/013866 JP2022013866W WO2022210240A1 WO 2022210240 A1 WO2022210240 A1 WO 2022210240A1 JP 2022013866 W JP2022013866 W JP 2022013866W WO 2022210240 A1 WO2022210240 A1 WO 2022210240A1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/003—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
- B29C70/12—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat
- B29C70/14—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat oriented
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
- B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
- B29C70/20—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in a single direction, e.g. roofing or other parallel fibres
- B29C70/205—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in a single direction, e.g. roofing or other parallel fibres the structure being shaped to form a three-dimensional configuration
- B29C70/207—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in a single direction, e.g. roofing or other parallel fibres the structure being shaped to form a three-dimensional configuration arranged in parallel planes of fibres crossing at substantial angles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
- B29C70/545—Perforating, cutting or machining during or after moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2793/00—Shaping techniques involving a cutting or machining operation
- B29C2793/009—Shaping techniques involving a cutting or machining operation after shaping
Definitions
- the present invention relates to moldings and processed products.
- Polyglycolic acid (PGA) is hydrolyzable and can have high mechanical strength. For this reason, moldings and processed products of polyglycolic acid (PGA) are suitable as members for downhole (underground drilling) tools for recovering hydrocarbon resources such as oil and gas from underground. Used. It is known to add a fiber filler such as glass fiber (GF) to a downhole tool member made of PGA from the viewpoint of increasing its mechanical strength (see, for example, Patent Document 1).
- GF glass fiber
- GF is sometimes used as a fiber filler in PGA moldings as downhole tool members, and the cross-sectional shape of GF is usually circular.
- the difference between the strength in the MD direction and the strength in the TD direction (also referred to as “strength anisotropy”) of the molding becomes large.
- Downhole tool members are generally exposed to high pressure environments in wells. For this reason, when using a PGA molded product as a downhole tool member, if the strength anisotropy of the PGA molded product is large, three-dimensionally complicated forces may act on the downhole tool member. be. As such, the durability of the downhole tool member may be insufficient, or a more sophisticated and complex design of the downhole tool member may be required.
- An object of one aspect of the present invention is to provide a molded product with low anisotropy and a processed product thereof.
- a molded product is a molded product containing a glycolic acid-based polymer and a plurality of fibers, wherein the fibers are oriented in a first direction. and the fibers oriented in a second direction that is a direction along a tangent to the circumference of a plurality of concentric circles having a common center in a cross section perpendicular to the first direction, and oriented in the first direction
- the ratio of the number of fibers oriented in the second direction to the number of fibers oriented is 0.2 to 5.0.
- a processed product according to one aspect of the present invention is a processed product manufactured by processing or molding the above molded product.
- FIG. 3 is a diagram schematically showing the arrangement of fibers oriented in the first direction indicated by MD among the fibers in the molded product according to one embodiment of the present invention.
- FIG. 4 is a diagram schematically showing the arrangement of fibers oriented in the MD direction in a cross section perpendicular to the MD direction of the molded product according to one embodiment of the present invention.
- FIG. 4 is a diagram schematically showing the arrangement of fibers oriented in the TD1 direction in a cross section orthogonal to the MD direction of a molded article according to one embodiment of the present invention.
- FIG. 4 is a diagram schematically showing the arrangement of fibers oriented in the first direction indicated by MD, among the fibers in a molded article for comparison.
- FIG. 3 is a diagram schematically showing the arrangement of fibers oriented toward one point in a cross section orthogonal to the MD direction, indicated by TD2, among fibers in a comparative molding.
- FIG. 4 is a diagram schematically showing the arrangement of fibers oriented in the MD direction in a cross section orthogonal to the MD direction of a comparative molded product.
- FIG. 4 is a diagram schematically showing the arrangement of fibers oriented in the TD1 direction in a cross section orthogonal to the MD direction of a molded article according to one embodiment of the present invention.
- FIG. 4 is a diagram schematically showing the arrangement of fibers
- FIG. 10 is a diagram schematically showing the arrangement of fibers oriented in the TD2 direction in a cross section perpendicular to the MD direction of a molded product for comparison.
- FIG. 4 is a diagram for explaining the orientation of the processed product with respect to the molded product in the embodiment of the present invention;
- FIG. 10 is an electron micrograph showing an example of the state of fibers when the processed product in one example of the present invention is viewed along arrow A in FIG. 9 ;
- FIG. FIG. 10 is an electron micrograph showing an example of the appearance of fibers when the processed product in one example of the present invention is viewed along arrow B in FIG. 9 ;
- FIG. 5 is a diagram for explaining the orientation of the processed product with respect to the molded product in one comparative example of the present invention
- FIG. 13 is an electron micrograph showing an example of the state of fibers when a processed product in a comparative example of the present invention is viewed along arrow A in FIG. 12
- FIG. 10 is an electron micrograph showing an example of the appearance of fibers when a processed product in another example of the present invention is viewed along arrow A in FIG. 9
- FIG. FIG. 10 is an electron micrograph showing an example of the appearance of fibers when a processed product in another example of the present invention is viewed along arrow B in FIG. 9
- Moldings of embodiments of the present invention contain a glycolic acid-based polymer and a plurality of fibers.
- a glycolic acid-based polymer is a polymer compound containing a glycolic acid unit (--OCH 2 --CO--) as a repeating unit.
- the glycolic acid-based polymer may be a glycolic acid homopolymer (that is, polyglycolic acid (PGA)) consisting only of glycolic acid units, or may be a copolymer further containing repeating units derived from other monomers. There may be.
- repeating units examples include hydroxylcarboxylic acid units such as lactic acid, and aliphatic polyesters such as polycaprolactone and polylactic acid.
- the content of other repeating units in the glycolic acid-based polymer may be 50% by mass or less, preferably 30% by mass or less, and more preferably 10% by mass or less. By employing other repeating units, it is possible to adjust the physical properties of the glycolic acid-based polymer, such as hydrolysis rate or crystallinity.
- the molecular weight of the glycolic acid-based polymer may be appropriately determined according to the use of the molded product and processed product. For example, in the case where the molded or processed product is used as a downhole tool member, if the molecular weight of the glycolic acid-based polymer is too low, the strength may be insufficient, and if it is too high, the molding processability may be insufficient. can be. From the viewpoint of expressing strength according to the application and realizing good moldability, the weight-average molecular weight of the glycolic acid-based polymer is preferably 70,000 or more, more preferably 100,000 or more. , and preferably 500,000 or less.
- a glycolic acid-based polymer can be produced by a known method.
- a glycolic acid-based polymer can be prepared by converting glycolide, which is a dimer of glycolic acid, at about 120 to 250° C. in the presence of a small amount of a catalyst and under conditions in which a solvent is substantially absent (that is, bulk polymerization conditions). It can be suitably produced by ring-opening polymerization.
- Examples of the above catalysts include cationic catalysts such as organic tin carboxylates, tin halides and antimony halides.
- the copolymer can be produced by the above method by using glycolide in combination with a comonomer.
- Examples of comonomers include lactides and lactones, typified by lactide, a dimer of lactic acid.
- Examples of lactones include caprolactone, ⁇ -propiolactone and ⁇ -butyrolactone.
- the fiber shape of a fiber can be represented by the ratio of fiber length to fiber diameter (major diameter) (fiber shape aspect ratio).
- the aspect ratio of the fiber shape of the fibers is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more.
- the aspect ratio of the fiber shape of the fibers is preferably 1000 or less, more preferably 300 or less, and even more preferably 200 or less.
- the type of fiber can be appropriately selected according to the application of the molded product and processed product, and may be of one type or more.
- fibers include inorganic fibers and organic fibers, more specifically cellulosic fibers such as glass fibers, carbon fibers, boron fibers, aramid fibers, liquid crystal polymer fibers, and kenaf fibers.
- the content of the above-mentioned fibers in the molded product can be appropriately determined within the range in which the effect of the fiber is exhibited according to the application of the molded product and processed product.
- the content of fibers in the molded product is preferably 1 part by mass or more with respect to 100 parts by mass of the glycolic acid-based polymer. It is more preferably at least 10 parts by mass, and even more preferably at least 10 parts by mass.
- the content of fibers in the molded product is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, relative to 100 parts by mass of the glycolic acid-based polymer for the above applications. It is more preferably 40 parts by mass or less.
- the cross-sectional shape of the fibers is not limited.
- the fibers preferably have a flat cross-sectional shape from the viewpoint of realizing the orientation of the fibers, which will be described later.
- the "flat cross-sectional shape" may be any shape as long as the fiber can exhibit the flow characteristics of a substantially flat filler in the molten resin.
- a flat cross-sectional shape can be expressed by the ratio of the major axis to the minor axis of the cross-sectional shape (aspect ratio of the cross-sectional shape).
- the aspect ratio of the cross-sectional shape of the fiber is preferably 1.5 or more, more preferably 2 or more, and even more preferably 4 or more.
- the aspect ratio of the cross-sectional shape of the fibers is preferably 1000 or less, more preferably 100 or less.
- the aspect ratio of the cross-sectional shape of the fiber may be obtained from the cross-sectional shape of the fiber as it is, or may be obtained from the image of the fiber cross-section that has been processed to express the shape more simply.
- the aspect ratio of the cross-sectional shape of the fiber is the ratio of the two adjacent sides of a rectangle that circumscribes the fiber cross section and has one or more external points of contact on all sides, and the ratio of the long side to the short side in the case of a rectangle. Desired.
- the diameter of the fiber having a flat cross-sectional shape is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, and more preferably 5 ⁇ m or more, in terms of the major axis, from the viewpoint of improving the strength of the molded product using the fiber. It is even more preferable to have
- the diameter of the fiber having a flat cross-sectional shape is preferably 1000 ⁇ m or less, more preferably 100 ⁇ m or less, and further preferably 50 ⁇ m or less, in terms of long axis, from the viewpoint of expressing good moldability. preferable.
- fibers having a flattened cross-sectional shape include fibers oriented in a first direction and fibers oriented in a second direction.
- the second direction can be defined by a relationship to the first direction and has a common center when the molding is viewed along the first direction, i.e. in a cross section perpendicular to the first direction The direction along the tangent to the circumference of a plurality of concentric circles.
- the concentric circles are a group of circles having a common center, and the second direction is determined for each group of concentric circles.
- the molded product may contain two or more groups of concentric circles, but it is preferable to include one group of concentric circles from the viewpoint of sufficiently expressing the desired strength of the fibers of the molded product.
- the fibers should be substantially oriented in the first direction with respect to the first direction.
- fibers that are oriented in a first direction may have an inclination of the long axis of the fiber with respect to the first direction of 30° or less.
- the fibers may be substantially oriented in the second direction relative to the second direction, e.g. may be 30° or less.
- the "long axis of the fiber" represents the dimension in the length direction of the fiber, and is, for example, a straight line connecting both ends of the fiber.
- the first direction, the second direction, and the number of fibers oriented in the directions described later can be determined by industrial X-ray computed tomography and, if necessary, information processing technology for fibers in the image. By using them together, it is possible to confirm from the molded product or the processed product.
- the first direction since the first direction may be the direction in which the resin material is supplied during molding of the molded product, the first direction can be determined by observing the cross section along the MD of the molded product. It is possible to confirm each by observing a cross section along TD.
- the direction in which the resin material is supplied is the direction in which the resin flows when the heated and melted resin is injected into the mold.
- a fiber whose length in the cross-sectional shape of the fiber on the viewing plane is less than twice the length in the actual cross-sectional shape of the fiber is counted as a fiber oriented perpendicular to the viewing plane.
- the length of the fiber in the cross-sectional shape of the viewing surface is twice or more the length of the fiber in the actual cross-sectional shape of the fiber, it is counted as a fiber oriented parallel to the viewing surface.
- the first direction and the second direction can be confirmed by observing cross-sections of the molding or work piece at various angles.
- the number of fibers oriented perpendicular to the observation surface is 6 compared to the number of fibers oriented parallel to the observation surface. .46 times more observed. Therefore, when counting the number of fibers by observing the first direction and the second direction with a microscope, the number of cross sections of the fibers actually counted on the observation surface is corrected by 6.46 times. and the number of fibers oriented in the second direction. That is, in this specification, the number of fibers oriented substantially parallel to a viewing plane is the value obtained by multiplying the measured value counted at that viewing plane by 6.46.
- the ratio of the number of fibers oriented in the second direction to the number of fibers oriented in the first direction is 0.2 to 5.0 in a group of concentric circles having a common center. is.
- the number ratio of the fibers is preferably 1.0 to 3.0, more preferably 1.0 to 2.0, from the viewpoint of further reducing the anisotropy of strength.
- the ratio of the sum of the number of fibers oriented in the first direction and the number of fibers oriented in the second direction to the total number of fibers is preferably 0.5 or more.
- the above ratio of the total number of oriented fibers to the total number of fibers is preferably larger from the viewpoint of increasing the strength of the molding in relation to the reduced anisotropy.
- the mass of the fibers oriented in the first direction and the mass of the fibers oriented in the second direction are preferably 10 parts by mass or more with respect to 100 parts by mass of the glycolic acid-based polymer.
- the shape of the molding is not limited and can be determined as appropriate.
- the orientation of the fibers described above can be realized by the flow of the resin material during molding of the molding. Therefore, the shape of the molded product is preferably a shape formed by flowing the resin material over a distance sufficient for orientation of the fibers.
- the shape of the molded product is preferably an elongated shape having a sufficiently large length relative to the cross-sectional dimension, and more specifically preferably a columnar shape.
- the resin material is preferably supplied in the longitudinal direction of the cylindrical shape from one end of the cylindrical shape during molding from the viewpoint of realizing the orientation of the fibers in the two directions described above. Therefore, the first direction is preferably a direction along the central axis of the cylindrical shape.
- the above-described concentric circles have a common center at the center of the cylindrical cross section of the molding.
- the molded article may further contain other materials other than the above-described glycolic acid-based polymer and fibers having a flat cross-sectional shape, as long as the effects of the embodiments of the present invention can be obtained. good.
- One or more other materials may be used, as long as they are used in such an amount that the effects of the other materials can be further exhibited.
- the molded article may further contain a thermoplastic resin other than the glycolic acid-based polymer.
- a thermoplastic resin other than the glycolic acid-based polymer.
- other thermoplastic resins include aliphatic polyesters other than glycolic acid-based polymers, aromatic polyesters, polyacrylic acid-based core-shell rubbers, and elastomers.
- the content of the other thermoplastic resin in the molded article is preferably less than 30% by mass, more preferably less than 20% by mass, from the viewpoint of sufficiently expressing the effect of the glycolic acid-based polymer, and 10% by mass. % is more preferable.
- the molding may further contain a sizing agent for bundling the fibers.
- the sizing agent can be used from the viewpoint of improving the handleability of fibers in the production of molded products, or from the viewpoint of increasing the mechanical strength of molded products.
- Examples of materials that make up the sizing agent include epoxy resins, urethane resins, acrylic resins, silane coupling agents and vinyl acetate resins. Among them, an epoxy resin is preferable from the viewpoint of increasing the strength of the molded product.
- the amount of the sizing agent used is preferably 0.1 to 10.0% by mass, more preferably 0.3 to 5.0% by mass, based on the total amount of the sizing agent and the fibers bundled by it. preferable.
- the molded product may further contain other fibers that do not have a flat cross-sectional shape. It can be used from the viewpoint of increasing the mechanical strength of the molded product or from the viewpoint of adjusting the anisotropy of the strength of the molded product. The strength anisotropy in the molding will be described in detail later.
- Other fibers can be selected from known fibers used for reinforcing resin compositions, and one or more of them may be used. Examples of other fibers include fibers having a substantially circular cross-section.
- the molded article may further contain additives within the range where the effects of the embodiments of the present invention can be obtained.
- Additives may be one or more, examples of which include heat stabilizers, light stabilizers, plasticizers, moisture barriers, waterproofing agents, water repellents, lubricants, antioxidants, decomposition accelerators and decomposition retardants. included.
- the molding of the embodiment of the present invention is made by mixing a glycolic acid-based polymer and fibers, and using the obtained resin material, during molding, the fibers are oriented as described above in the continuous phase of the glycolic acid-based polymer. It is possible to manufacture by molding under conditions to sufficiently flow. From the viewpoint of orienting the fibers as described above, it is preferable to manufacture the molded product by a molding method in which the resin material is supplied at a sufficiently low speed during molding. Examples of such molding methods include extrusion.
- the targeted fiber orientation can be achieved by slowing down the extrusion speed, and although it cannot be said unconditionally, from the viewpoint of orienting a sufficient number of fibers in the second direction , when using fibers having a flattened cross-sectional shape, it may be from 50 to 150 mm/h. From the viewpoint of orienting a sufficient number of fibers in the second direction, it is preferable to use fibers having a flat cross-sectional shape as the fibers in the production of the molded product.
- the extrusion speed cannot be generalized, in the case of using fibers having a circular cross-sectional shape, from the viewpoint of orienting a sufficient number of fibers in the second direction, it may be 50 to 120 mm / hour. .
- the flow rate of the resin material during molding can be appropriately controlled according to the shape of the molded product, molding methods other than extrusion molding, such as injection molding, can also be used. can be formed.
- molding methods other than extrusion molding such as injection molding, can also be used.
- the above-mentioned molded article with specifically oriented fibers can be obtained. can be formed.
- the molded product of the embodiment of the present invention exhibits biodegradability due to the glycolic acid-based polymer and mechanical strength with low anisotropy due to the fibers showing a specific orientation. It is preferably used.
- a downhole tool member is mentioned below.
- a processed product according to the embodiment of the present invention is a product manufactured by processing the molded product according to the embodiment of the present invention described above. Since the processed product of the present embodiment is obtained using the molded product as a raw material, the above-described characteristic orientation of the fibers is observed from the processed product.
- the processed product in the embodiment of the present invention can be manufactured by processing the molded product described above. Examples of the processing include cutting.
- the processed product in the embodiment of the present invention can also be manufactured by molding using the above-described molded product as a material.
- a processed product obtained by processing a molded product is also referred to as a "secondary molded product".
- the molding method for manufacturing the secondary molding may be any method that allows the characteristic orientation of the fibers described above to be substantially maintained in the secondary molding, examples of which include cutting.
- the processed product in the embodiment of the present invention may be a secondary molded product.
- the molded product may be a secondary molded product obtained by further molding the above-described molded product.
- the molding conditions for producing the secondary molded product can be appropriately determined within a range in which the aforementioned orientation of the fibers in the molded product can be substantially retained.
- the conditions for the press molding are not general, but the above-mentioned fiber orientation in the molded product is substantially maintained.
- the condition may be a molding pressure of 50 kN or less. In this case, the above-mentioned orientation of the fibers is observed in the secondary moulding, substantially depending on the morphology of the original moulding.
- the production of the processed product may further include steps other than the above-described molding or processing within the range in which the effects of the embodiments of the present invention can be obtained.
- a heat treatment annealing treatment
- a stress relaxation of the workpiece after molding or processing may be further performed.
- the processed product in the embodiment of the present invention is suitable for downhole tool members.
- Downhole tools are instruments used for the recovery of hydrocarbon resources, such as oil and gas, from underground. Examples of downhole tools include flack plugs, bridge plugs, cement retainers, perforation guns, ball sealers, filler plugs, and packers.
- the downhole tool is used for a predetermined time in a working environment aqueous medium at a predetermined temperature of, for example, 20 to 180 ° C. for work such as downhole formation, repair or expansion, and then disintegrates and is removed. It is designed so that it can be
- the temperature of the surrounding environment of the downhole tool member is increased, for example, by injecting heated steam or by reducing the supply amount of working water for fracturing. It is possible to As a result, it is possible to accelerate the hydrolytic disintegration of the downhole tool member.
- FIG. 1 is a diagram schematically showing the arrangement of fibers oriented in a first direction indicated by MD among fibers in a molded product according to one embodiment of the present invention.
- FIG. 2 shows, among the fibers in the molded article according to one embodiment of the present invention, a plurality of concentric circles having a common center when viewed along the MD direction, indicated by TD1.
- FIG. 4 is a diagram schematically showing the arrangement of oriented fibers;
- FIG. 3 is a diagram schematically showing the arrangement of fibers oriented in the MD direction in a cross section perpendicular to the MD direction of a molded product according to one embodiment of the present invention.
- FIG. 4 is a diagram schematically showing the arrangement of fibers oriented in the TD1 direction in a cross section orthogonal to the MD direction of a molded product according to one embodiment of the present invention.
- the molding 10 has a cylindrical shape as an example, and fibers 11 are dispersed in a specific orientation in the continuous phase of the glycolic acid-based polymer.
- the fibers 11 are, for example, fibers having a flat cross-sectional shape (for example, glass fibers).
- the arrow MD represents the direction of supply of the resin material during molding of the molding 10
- the arrows TD1 and TD2 represent directions orthogonal to the direction of supply.
- Arrow TD1 represents the direction along the tangential line of the circumference of a plurality of concentric circles having a common center when viewed along the MD direction, as described above.
- An arrow TD2 represents a direction perpendicular to both the MD direction and the TD1 direction.
- Molded article 10 is manufactured, for example, by extrusion molding.
- the "supply direction of the resin material during molding of the molded product 10" is determined by observing the cross section of the molded product 10 with an electron or optical microscope and observing traces (such as flow marks) indicating the direction in which the resin flowed during molding. It is possible by checking
- the fibers 11 are mainly dispersed in one of two directions.
- the first direction is the direction along the MD direction.
- the second direction is a direction along the circumference of a plurality of concentric circles having the center O as a common center when the molding 10 is viewed from a direction orthogonal to the MD direction.
- the center O of the concentric circles is located at the center of the end surface or cross section of the molded product 10, and corresponds to the position of the tip of the resin material supplied during molding.
- the second direction is a direction along which a tangent line extends at an arbitrary position on the circumference of the concentric circles.
- the fibers 11 oriented in the first direction are distributed throughout the molding 10. This is considered to be oriented by supplying the resin material in the MD direction during molding. Therefore, when a force in the MD direction acts on the molded product 10, since the fibers 11 along the MD direction are present throughout the molded product 10, the force (external force or stress) acting in the MD direction causes the molded product 10 to deformation is suppressed. Thus, the strength of the molding 10 in the MD direction is enhanced by the fibers 11 oriented in the first direction.
- the second direction is the direction along the tangential line of the circumference of a plurality of concentric circles having a common center when the cross section of the molding is viewed along the MD direction. Therefore, a region including the center O (the central axis of the molded article 10) in the molded article 10 contains a component perpendicular to the MD direction.
- the orientation of the fibers 11 oriented in the second direction includes a component in the direction perpendicular to the MD direction, and such orientation fibers 11 are distributed throughout the molding 10 .
- the reason why the fibers 11 are oriented in the second direction is that some of the fibers 11 are oriented in the second direction due to the behavior peculiar to fibers having such a flat cross-sectional shape during molding. Conceivable.
- the value of the orientation parameter changes depending on the shape of the filler used. If it is fibrous, it is likely to be oriented in the same direction as the resin flow, and if it is flat, it is likely to be oriented in the direction perpendicular to the resin flow. As a result, it is believed that the flow characteristics of the substantially plate-like filler are exhibited in the molten resin, and the orientation of the fibers as specified in the embodiment of the present invention is realized.
- the molded product 10 is less likely to be deformed by force acting in the MD direction, and is also less likely to be deformed by force acting in the TD direction. Therefore, the molded article 10 has no or sufficiently small anisotropy in the MD and TD directions.
- Anisotropic generally means that properties change depending on the direction of molecular or fiber orientation.
- the anisotropy of moldings of embodiments of the present invention can be expressed by mechanical strength, and the magnitude of the anisotropy is expressed by the ratio of the mechanical strength in the MD direction to the mechanical strength in the TD direction. be able to. The closer the ratio is to 1, the smaller the anisotropy.
- a processed product obtained by processing the molded product also has the advantages of the above-described molded product within the range including the orientation of the fibers.
- the processed product can be preferably manufactured by cutting the molded product 10 so that the above-mentioned center O is included in the center of the shape when the processed product is viewed from any direction. be.
- the orientation of the fibers in the molding is substantially preserved.
- a specific one of the fibers oriented in the second direction of the molded product It may be manufactured using only the portion where fibers having a component oriented in the TD direction of are present.
- FIGS. 5 to 8 are diagrams schematically showing the arrangement of fibers in comparative moldings.
- FIG. 5 is a diagram schematically showing the arrangement of fibers oriented in the first direction indicated by MD among the fibers in the comparative molding.
- FIG. 6 is a diagram schematically showing the arrangement of fibers oriented toward one point when viewed along the MD direction, indicated by TD2, among the fibers in the molded article for comparison.
- FIG. 7 is a diagram schematically showing the arrangement of fibers oriented in the MD direction in a cross section perpendicular to the MD direction of a molded product for comparison.
- FIG. 8 is a diagram schematically showing the arrangement of fibers oriented in the TD2 direction in a cross section perpendicular to the MD direction of a molded article for comparison.
- the molding 20 has fibers 21, and the fibers 21 are glass fibers having a circular cross-sectional shape. Some of the fibers 21 are oriented along the MD direction, and some of the fibers 21 are oriented radially from the center of the cross section orthogonal to the MD direction. Such fiber orientation is considered to occur when the flow rate of the resin composition during molding is sufficiently high.
- the strength of the molding 20 in the MD direction is enhanced by the fibers 21 oriented in the MD direction.
- the fibers 21 oriented in the direction along the TD direction are oriented in the longitudinal direction of the fiber when the cross section of the molded product is viewed along the MD direction. Orient toward the center of the object. Therefore, in the molded article 20, the fibers that contribute to the suppression of deformation of the molded article 20 against the force acting in the TD1 direction are unevenly distributed and limited. Therefore, the molded product 20 is not sufficiently deformed by a force acting in the MD direction, but is more easily deformed by a force acting in the TD1 direction than in the MD direction.
- the anisotropy of the strength in the MD direction and the TD1 direction in the molded product 20 is greater than that in the molded product 10 .
- the cross-sectional shape of the fibers is not limited, the specific orientation of the fibers as described above is realized, and the MD direction of the molded article and the anisotropy of the mechanical strength in the TD direction is relaxed. More specifically, embodiments of the present invention relax the anisotropy of mechanical strength between the MD and any relative TD.
- the addition of fibers having a flat cross-sectional shape alleviates the anisotropy of the mechanical strength between the MD direction and an arbitrary TD direction. No report has been made.
- the molded product of the embodiment of the present invention has small anisotropy of mechanical strength in the MD direction and the TD direction as described above. Therefore, when used as a downhole tool member, or during processing for manufacturing the member, the need for design adjustment due to the anisotropy of mechanical strength is reduced.
- the molded article of the embodiment of the present invention is a molded article containing a glycolic acid-based polymer and a plurality of fibers, wherein the fibers are fibers oriented in the first direction and fibers oriented in the second direction.
- a fiber oriented in a second direction which is a direction along a tangent to the circumference of a plurality of concentric circles having a common center in a cross section orthogonal to one direction, and a fiber oriented in the first direction in the concentric circle
- the ratio of the number of fibers oriented in the second direction to the number of is between 0.2 and 5.0.
- the first direction is the direction in which the resin material is supplied during molding of the molding.
- the processed product of the embodiment of the present invention is a processed product manufactured by processing the molded product of the embodiment of the present invention. According to the embodiment of the present invention, it is possible to provide a molded product and a processed product thereof with small anisotropy of strength between the MD direction and the TD direction.
- the ratio of the sum of the number of fibers oriented in the first direction and the number of fibers oriented in the second direction to the total number of fibers may be 0.5 or more. This configuration is more effective from the viewpoint of enhancing the effect of alleviating the strength anisotropy in the MD direction and the TD direction.
- the shape of the molding is cylindrical
- the first direction is the direction along the central axis of the cylindrical shape
- the concentric circles have a common center at the center of the cross section of the cylindrical shape. may have. This configuration is more effective from the viewpoint of enhancing the effect of alleviating the strength anisotropy in the MD direction and the TD direction.
- the processed product may be a downhole tool member.
- the above-mentioned molded article with reduced strength anisotropy is suitable as a downhole tool member or a material thereof.
- Example 1 A material composition (compound) containing 70 parts by mass of PGA and 30 parts by mass of glass fiber (FF) having a flat cross-sectional shape was prepared.
- PGA a product with a weight average molecular weight of 200,000 manufactured by Kureha Co., Ltd. was used.
- the above compound was extruded using a twin-screw extruder to produce composite pellets containing PGA and FF at a mass ratio of 70:30.
- the temperature of the mold was set to 50° C., and the molding was performed under the conditions of cooling and solidification.
- the extrusion speed was about 17 mm/10 minutes.
- the forming die external pressure (back pressure) is adjusted to 30 kN, and solidified extrusion molding Suppressed the expansion of things.
- back pressure back pressure
- the molded product of this example is in the shape of a round bar, that is, in the shape of a cylinder.
- the MD direction in the molded product (processed product) is the direction along the central axis of the cylindrical shape.
- the TD1 direction is a direction in which tangent lines of concentric circles having a common center in a cylindrical cross section extend.
- FIG. 9 is a diagram for explaining the orientation of the processed product 1 with respect to the molded product.
- the cube in FIG. 9 has a pair of side surfaces orthogonal to the MD direction and two pairs of side surfaces parallel to the MD direction. The positional relationship between the two pairs of side surfaces parallel to the MD direction is such that the side surface of one pair is orthogonal to the side surface of the other pair.
- Arrow A in the drawing indicates the direction of viewing along the TD direction of the molded article
- arrow B in the drawing indicates the direction of viewing along the MD direction of the molded article.
- FIG. 10 is an electron micrograph showing an example of the state of fibers when the processed product 1 is viewed along arrow A in FIG.
- FIG. 11 is an electron micrograph showing an example of the appearance of fibers when the processed product 1 is viewed along arrow B in FIG.
- the direction perpendicular to the drawing is the TD1 direction.
- the vertical arrow in the drawing indicates the TD2 direction
- the horizontal arrow indicates the MD direction.
- the fibers in FIG. 10 are observed to have a short length, that is, many cross sections. Therefore, it can be seen from FIG. 10 that the fibers are oriented in the TD direction.
- the direction perpendicular to the drawing is the MD direction.
- An arrow pointing diagonally upward to the right of the drawing indicates the TD1 direction, and an arrow pointing diagonally upward to the left indicates the TD2 direction.
- All fibers in FIG. 11 are oriented in one oblique direction on the screen. Therefore, it can be seen from FIG. 11 that the fibers are oriented in a direction crossing the MD direction, ie, in the TD direction.
- Example 2 A molded product and a processed product 2 were produced in the same manner as in Example 1 except that instead of FF, a material composition (compound) containing glass fibers (GF) having a circular cross-sectional shape was used.
- GF glass fibers
- Example 1 A molding and a processed product C1 were produced in the same manner as in Example 2 except that the extrusion temperature was 255° C., the cooling mold temperature was 70° C., and the extrusion speed was 25 mm/10 minutes.
- FIG. 12 is a diagram for explaining the orientation of the processed product C1 with respect to the molded product.
- the cube in FIG. 12 has a similar orientation and shape as the cube shown in FIG.
- the arrow A in the figure represents the direction of viewing along the MD direction of the molding.
- FIG. 13 is an electron micrograph showing an example of the state of fibers when the processed product C1 is viewed along arrow A in FIG.
- the direction perpendicular to the drawing is the MD direction.
- a vertical arrow in the drawing indicates the TD2 direction, and a horizontal arrow indicates the TD1 direction.
- the fibers in FIG. 13 a group of fibers along the direction converging to one point outside the screen can be seen here and there. Therefore, it can be seen from FIG. 13 that the fibers are oriented in a direction converging at one point when viewed along the MD direction, that is, in a direction radially extending from the central point (TD2 direction).
- FIG. 14 is an electron micrograph showing an example of the appearance of fibers when the processed product 2 is viewed along arrow A in FIG.
- FIG. 15 is an electron micrograph showing an example of the appearance of fibers when the processed product 2 is viewed along arrow B in FIG.
- the direction perpendicular to the drawing is the TD1 direction.
- the vertical arrows in FIG. 14 indicate the TD2 direction, and the horizontal arrows indicate the MD direction.
- the direction perpendicular to the drawing is the MD direction.
- a vertical arrow in FIG. 15 indicates the TD2 direction, and a horizontal arrow indicates the TD1 direction.
- Processed product 2 contains GF, but similar to processed product 1, many cross sections of fibers are observed in FIG. 14, and fibers oriented in one direction in the screen are observed in FIG. Therefore, it can be seen that in the processed product 2, the fibers are oriented in the TD direction as in the processed product 1.
- Table 1 shows information on processed products 1 and 2 and processed product C1.
- the fiber diameter represents the approximate diameter for FF and the diameter for GF.
- “Ra” represents the aspect ratio
- the mixing ratio represents the ratio of the resin content to the fiber.
- N 2 /N 1 is the ratio of the number N 2 of fibers oriented in the TD1 direction to the number N 1 of fibers oriented in the MD direction.
- N 12 /N is the ratio of the sum N 12 of the number N 1 of fibers oriented in the MD direction and the number N 2 of fibers oriented in the TD 1 direction to the total number N of fibers.
- N 1 is fibers substantially oriented in the MD direction (MD direction ⁇ 30 6.46 times the average number of fibers per field of view.
- N 2 refers to fibers substantially oriented in the TD1 direction (TD1 direction ⁇ 30 6.46 times the average number of fibers per field of view.
- 6.46 is a coefficient for correcting the observed number of fibers oriented in a direction substantially parallel to the cross section, as described above. Also, the TD1 direction for each field of view can be obtained from the concentric circles by confirming the concentric orientation of the fibers in the cross section.
- 'N' is the mean of the total number of fibers observed in each field of view in the 'N 1 ' and 'N 2 ' measurements.
- Table 2 shows the above evaluation results.
- SMD represents the compressive strength in the MD direction
- STD1 represents the compressive strength in the tangential direction (TD1) of concentric circles centered on the cross section of the molding
- SMD /S TD1 represents the ratio of the compressive strength in the MD direction to the compressive strength in the TD1 direction.
- the ratio of the compressive strength in the MD direction to the compressive strength in the TD1 direction was 1.72 in the processed product C1, which was added with GF and molded at an extrusion speed of 25 mm/10 minutes.
- the ratio of the compressive strength in the MD direction to the compressive strength in the TD1 direction in the FF-added processed product 1 and the GF-added processed product 2 molded at an extrusion speed of 17 mm / 10 minutes is 0.88 and 1 .10. From this result, it was confirmed that slowing down the extrusion speed has the effect of alleviating the anisotropy.
- the anisotropy of mechanical strength is suppressed in the molding that is the material of the downhole tool member. Therefore, the present invention is expected to contribute to the extension of the life of the member and the improvement of productivity.
Abstract
Description
本発明の実施形態の成形物は、グリコール酸系ポリマーおよび複数の繊維を含有する。
グリコール酸系ポリマーは、繰り返し単位としてグリコール酸単位(-OCH2-CO-)を含む高分子化合物である。グリコール酸系ポリマーは、グリコール酸単位のみからなるグリコール酸単独重合体(すなわちポリグリコ-ル酸(PGA))であってもよいし、他の単量体由来の繰り返し単位をさらに含む共重合体であってもよい。
本発明の実施形態において、繊維の繊維形状は、繊維径(長径)に対する繊維長の比(繊維形状のアスペクト比)で表すことができる。成形物の強度を高める観点から、上記繊維における繊維形状のアスペクト比は、2以上であることが好ましく、3以上であることがより好ましく、4以上であることがさらに好ましい。また、成形物における繊維の分散性を高める観点から、上記繊維における繊維形状のアスペクト比は、1000以下であることが好ましく、300以下であることがより好ましく、200以下であることがさらに好ましい。
本発明の実施形態において、扁平な断面形状を有する繊維は、第一の方向に配向する繊維と第二の方向に配向する繊維とを含む。第二の方向は、第一の方向との関係によって決めることができ、成形物を第一の方向に沿って見たときに、すなわち第一の方向に直交する断面において、共通の中心を有する複数の同心円の円周の接線に沿う方向である。
本発明の実施形態において、成形物の形状は限定されず、適宜に決めることが可能である。前述した繊維の配向は、成形物の成形時における樹脂材料の流動によって実現され得る。よって、成形物の形状は、繊維の配向に十分な距離を樹脂材料が流動することで形成される形状であることが好ましい。
本発明の実施形態において、成形物は、本発明の実施形態の効果が得られる範囲において、前述したグリコール酸系ポリマーおよび扁平な断面形状を有する繊維以外の他の材料をさらに含有していてもよい。他の材料は、一種でもそれ以上でもよく、他の材料による効果がさらに発現され得る量で用いればよい。
本発明の実施形態の成形物は、グリコール酸系ポリマーおよび繊維を混合し、得られた樹脂材料を用いて、成形時にグリコール酸系ポリマーの連続相中で前述のような配向となるように繊維を十分に流動させる条件で成形することによって製造することが可能である。繊維を上記のように配向させる観点から、成形時における樹脂材料の供給速度が十分に低い成形方法によって成形物を製造することが好ましい。このような成形方法の例には、押出成形が含まれる。押出成形の条件は、押出速度を遅くすることにより狙いとする繊維配向の実現が可能であると推測され、一概には言えないが、十分な数の繊維を第二の方向に配向させる観点から、扁平な断面形状を有する繊維を用いる場合では、50~150mm/時であってよい。また、十分な数の繊維を第二の方向に配向させる観点から、上記の成形物の製造において、繊維には扁平な断面形状を有する繊維を用いることが好ましい。また、押出速度は、一概には言えないが、円形の断面形状を有する繊維を用いる場合では、十分な数の繊維を第二の方向に配向させる観点から、50~120mm/時であってよい。
本発明の実施形態の成形物は、グリコール酸系ポリマーによる生分解性と、特定の配向を示す繊維による異方性が低い機械的強度とを発現することから、ダウンホールツール部材またはその原料に好適に用いられる。ダウンホールツール部材については後述する。
本発明の実施形態における加工品は、前述した本発明の実施形態の成形物の加工により製造された物である。本実施形態の加工品は、当該成形物を原料として得られることから、当該加工品からは、前述した繊維の特徴的な配向が観察される。
以下、本発明の実施形態における強度の異方性についてより詳しく説明する。図1は、本発明の一実施形態に係る成形物における繊維のうち、MDで示される第一の方向に配向する繊維の配置を模式的に示す図である。図2は、本発明の一実施形態に係る成形物における繊維のうち、TD1で示される、MD方向に沿って見たときに共通の中心を有する複数の同心円の円周の接線に沿う方向に配向する繊維の配置を模式的に示す図である。図3は、本発明の一実施形態に係る成形物の、MD方向に直交する断面におけるMD方向に配向する繊維の配置を模式的に示す図である。図4は、本発明の一実施形態に係る成形物の、MD方向に直交する断面におけるTD1方向に配向する繊維の配置を模式的に示す図である。
以上の説明から明らかなように、本発明の実施形態の成形物は、グリコール酸系ポリマーおよび複数の繊維を含有する成形物であって、繊維は、第一の方向に配向する繊維と、第一の方向に直交する断面における共通の中心を有する複数の同心円の円周の接線に沿う方向である第二の方向に配向する繊維とを含み、当該同心円において、第一の方向に配向する繊維の数に対する、第二の方向に配向する繊維の数の比は、0.2~5.0である。ここで、第一の方向は成形物の成形時における樹脂材料の供給方向である。また、本発明の実施形態の加工品は、本発明の実施形態における成形物の加工により製造された加工品である。本発明の実施形態によれば、MD方向とTD方向との強度の異方性が小さい成形物およびその加工品を提供することができる。
70質量部のPGAと、扁平な断面形状を有する30質量部のガラス繊維(FF)とを含有する材料組成物(コンパウンド)を用意した。
FFに代えて、円形の断面形状を有するガラス繊維(GF)を含有する材料組成物(コンパウンド)を用いる以外は実施例1と同様にして成形物および加工品2を作製した。GFには、オーウェンスコーニング社製(CS03JAFT562PB25KI、繊維長3.2mm、繊維径10μm)を使用した。
押出温度255℃、冷却金型の温度を70℃、押出速度を25mm/10分とする以外は実施例2と同様にして、成形物および加工品C1を製造した。
[成形物から切削した加工品の圧縮強度の測定]
加工品1、2および加工品C1のそれぞれについて、MD方向に直交する一対の面で加工品を圧縮することにより、MD方向の圧縮強度を測定した。また、MD方向に沿う二対の面のうち、TD1の方向からの圧縮強度を測定した。圧縮強度は、23℃の条件下で試験速度1mm/minで圧縮荷重を加え、加工品が破断した際の最大点応力を測定した。
11、21 繊維
Claims (5)
- グリコール酸系ポリマーおよび複数の繊維を含有する成形物であって、
前記繊維は、第一の方向に配向する前記繊維と、前記第一の方向に直交する断面における共通の中心を有する複数の同心円の円周の接線に沿う方向である第二の方向に配向する前記繊維とを含み、
前記同心円において、前記第一の方向に配向する前記繊維の数に対する、前記第二の方向に配向する前記繊維の数の比は、0.2~5.0であり、
前記第一の方向は成形物の成形時における樹脂材料の供給方向である、成形物。 - 前記繊維の総数に対する、前記第一の方向に配向する前記繊維の数および前記第二の方向に配向する前記繊維の数の和の比は、0.5以上である、請求項1に記載の成形物。
- 円柱状であり、
前記第一の方向は、円柱形状の中心軸に沿う方向であり、
前記同心円は、円柱形状の断面における中心部に共通の中心を有する、
請求項1または2に記載の成形物。 - 請求項1~3のいずれか一項に記載の成形物の加工により製造された加工品。
- ダウンホールツール部材である、請求項4に記載の加工品。
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008138049A (ja) * | 2006-11-30 | 2008-06-19 | Mitsubishi Rayon Co Ltd | ポリエステル樹脂組成物およびポリエステル成形体 |
JP2013112751A (ja) * | 2011-11-29 | 2013-06-10 | Mitsubishi Engineering Plastics Corp | 芳香族ポリカーボネート樹脂組成物及びそれからなる成形品 |
WO2014010267A1 (ja) | 2012-07-10 | 2014-01-16 | 株式会社クレハ | 炭化水素資源回収ダウンホールツール用部材 |
WO2014077302A1 (ja) * | 2012-11-15 | 2014-05-22 | 株式会社クレハ | ポリグリコール酸固化押出成形物及びその製造方法 |
WO2014092067A1 (ja) * | 2012-12-12 | 2014-06-19 | 株式会社クレハ | ポリグリコール酸固化押出成形物及びその製造方法 |
CN107903599A (zh) * | 2017-12-14 | 2018-04-13 | 陈逊 | 一种聚乙醇酸树脂挤出复合材料及其制造方法 |
US20180313184A1 (en) * | 2016-01-11 | 2018-11-01 | Halliburton Energy Services, Inc. | Extrusion limiting ring for wellbore isolation devices |
JP2019060219A (ja) * | 2017-09-22 | 2019-04-18 | 株式会社クレハ | ダウンホールツール部材及びその製造方法 |
WO2020087216A1 (en) * | 2018-10-29 | 2020-05-07 | Pujing Chemical Industry Co., Ltd | Polyglycolic acid copolymer composition and preparation thereof |
-
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Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008138049A (ja) * | 2006-11-30 | 2008-06-19 | Mitsubishi Rayon Co Ltd | ポリエステル樹脂組成物およびポリエステル成形体 |
JP2013112751A (ja) * | 2011-11-29 | 2013-06-10 | Mitsubishi Engineering Plastics Corp | 芳香族ポリカーボネート樹脂組成物及びそれからなる成形品 |
WO2014010267A1 (ja) | 2012-07-10 | 2014-01-16 | 株式会社クレハ | 炭化水素資源回収ダウンホールツール用部材 |
WO2014077302A1 (ja) * | 2012-11-15 | 2014-05-22 | 株式会社クレハ | ポリグリコール酸固化押出成形物及びその製造方法 |
WO2014092067A1 (ja) * | 2012-12-12 | 2014-06-19 | 株式会社クレハ | ポリグリコール酸固化押出成形物及びその製造方法 |
US20180313184A1 (en) * | 2016-01-11 | 2018-11-01 | Halliburton Energy Services, Inc. | Extrusion limiting ring for wellbore isolation devices |
JP2019060219A (ja) * | 2017-09-22 | 2019-04-18 | 株式会社クレハ | ダウンホールツール部材及びその製造方法 |
CN107903599A (zh) * | 2017-12-14 | 2018-04-13 | 陈逊 | 一种聚乙醇酸树脂挤出复合材料及其制造方法 |
WO2020087216A1 (en) * | 2018-10-29 | 2020-05-07 | Pujing Chemical Industry Co., Ltd | Polyglycolic acid copolymer composition and preparation thereof |
Non-Patent Citations (1)
Title |
---|
NOMURAKANNOYAMAO ET AL.: "Influence of Shape of Cross Section on Properties of GF Reinforced Thermo-Plastics", JOURNAL OF THE JAPAN SOCIETY OF COMPOSITE MATERIALS, vol. 36, no. 6, 2010, pages 230 - 236 |
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