WO2015098803A1 - Degradable resin composition for solidification and extrusion molding, molded product, secondary molded product, downhole tool or member, and method for recovering hydrocarbon resources - Google Patents

Abstract

Disclosed is a degradable resin composition for solidification and extrusion molding, the resin composition including 60-97 mass% of a degradable resin, 3-37 mass% of a reinforcement material, and 0-3.5 mass% of a toughness improving agent (100 mass% in total of the degradable resin, the reinforcement material, and the toughness improving agent), the resin composition having an Izod impact strength (no notch) of 500 J/m or greater, an Izod impact strength (notched) of 50 J/m or greater, and a tensile strength of 135 MPa or greater. Also disclosed are: a solidified-and-extruded degradable resin molded product and secondary molded product formed from said degradable resin composition for solidification and extrusion molding; a downhole tool or a member thereof formed from the resin (secondary) molded product; and a method for recovering hydrocarbon resources.

Description

Decomposable resin composition for solidification extrusion molding, molded product, secondary molded product, downhole tool or member, and hydrocarbon resource recovery method

The present invention relates to a decomposable resin composition for solidification extrusion molding, and more particularly, a decomposability for solidification extrusion molding suitable for forming a molded product or a secondary molded product, particularly a downhole tool for well excavation or a member thereof. The present invention relates to a resin composition, a solidified extrusion-decomposable resin molded product, a solidified extrusion-decomposable resin secondary molded product, a downhole tool or a member thereof, and a hydrocarbon resource recovery method.

A resin molded product having a three-dimensional shape or a complicated shape is generally formed by injection molding. According to injection molding, a molded product having a desired shape can be mass-produced. However, in order to produce a molded product requiring high dimensional accuracy by injection molding, an extremely expensive mold having a predetermined shape with high dimensional accuracy is required. Moreover, since the injection-molded product is easily deformed due to shrinkage and residual stress after injection molding, it is necessary to precisely adjust the mold shape according to the shape of the molded product and the characteristics of the resin material. Furthermore, in injection molding, since the defect rate is high, the cost of the product is often high, and since there is shrinkage and residual stress, it is difficult to mold a molded product having a large thickness.

[Machining materials]
In order to obtain a molded product having a three-dimensional shape or a complicated shape, a material for machining, which is a resin molded product having various cross-sectional shapes such as flat plates, round bars, pipes, and odd-shaped products by extrusion molding of a resin material (“ Known as a “cutting material”), and a machined material such as cutting, drilling or cutting is formed on the machining material to form a secondary molded product having a desired shape. ing. The machining method for machining materials does not require expensive molds, so that it is possible to manufacture molded products with a small production volume at a relatively low cost, to respond to frequent changes in the specifications of the molded products, and to improve dimensional accuracy. Advantages include that a high molding can be obtained and that a molding having a complicated shape and a large thickness that are not suitable for injection molding can be produced.

す べ て Not all resin materials and extruded products are suitable for machining materials. For machining materials, for example, thickness is excellent in machining suitability, residual stress is small, excessive heat is not generated due to frictional heat generated during machining, deformation and discoloration, and machining with high accuracy It is required to satisfy a high degree of required characteristics such as being able to do so.

That is, most of the processing methods used for metal materials are generally used as they are for machining of polymer resin materials. Of extruded products, thin and highly flexible materials such as ordinary films, sheets and tubes are not suitable for machining such as cutting. Even if the extruded product has a shape such as a flat plate or round bar with a large thickness or diameter, the extruded product with excessive residual stress during extrusion is easily deformed at the time of machining or after machining, and has a high dimensional accuracy. It is difficult to obtain a high secondary molded product. Even extruded products with reduced residual stress are not suitable for machining materials if they are prone to cracking or cracking during machining such as cutting, drilling or cutting.

In order to obtain a machining material having characteristics suitable for machining by extrusion molding, it is necessary to devise a selection of a resin material and an extrusion molding method suitable for the resin material. Therefore, conventionally, various proposals have been made on a molding method for producing an extruded product suitable for a machining material using a resin material containing general-purpose resin or engineering plastic.

For example, Patent Document 1 discloses that a resin composition containing an engineering plastic such as polyether ether ketone, polyether imide, polyphenylene sulfide, polysulfone, polyether sulfone, or polycarbonate is solidified and extruded to have a thickness or diameter exceeding 3 mm. A method of manufacturing a machining material having the following is disclosed.

Here, solidification extrusion molding involves a process of melting a resin material and extruding it from a heating shaping mold, so it may be included in a broad sense of extrusion molding, but a heating shaping mold and a cooling shaping mold. Is a molding method different from so-called extrusion molding in that it is cooled and solidified in a cooling shaping mold while a high back pressure during extrusion is applied to the resin material, and the molded product is drawn out. Solidified extrusion molding is a molding method that is distinguished from extrusion molding in that the molding speed is extremely small, for example, several mm to several tens mm / 10 minutes. Solidified extrusion molding has been attracting attention as a molding method for producing a machining material as described above.

Solidification extrusion molding is a molding performed under a high back pressure, so that unique problems are known such that it is desired to perform molding with as low a torque as possible by improving the melting characteristics of the resin material. In addition, when a solidified extruded resin molded product formed by solidified extrusion molding is used as a machining material, there is no cracking or deformation during machining, and the solidified extruded resin secondary molded product formed by machining is It has been desired to have a high dimensional accuracy and to prevent deformation and distortion.

(Degradable resin)
On the other hand, degradable resins have attracted attention as environmentally friendly polymer materials, and their use has been expanded to extrusion moldings such as films and sheets, blow moldings such as bottles, and injection moldings. Known degradable resins include aliphatic polyesters such as polylactic acid, polyglycolic acid, and poly-ε-caprolactone. For example, polyglycolic acid is a crystalline resin excellent in tensile strength, tensile elongation, bending strength, flexural modulus, hardness, flexibility, heat resistance, etc., and comparable to general-purpose gas barrier resins. It is a degradable resin that has superior gas barrier properties. Patent Document 2 discloses a method of forming polyglycolic acid into a sheet by extrusion molding. The sheet has a thickness of 0.01 to 5 mm, and it is disclosed that various sheet molded products are produced by taking advantage of characteristics such as toughness, heat resistance, and transparency.

In recent years, there has been an increasing demand for the application of degradable resins to machining materials. For example, Patent Document 3 discloses a polyglycolic acid-solidified extruded resin molded product having a thickness or diameter of 5 to 100 mm obtained by solidifying and extrusion-molding polyglycolic acid. In Patent Document 3, if the thickness or diameter is too large, it is difficult to sufficiently remove or reduce the residual stress. When a solidified extruded resin molded product having a large residual stress is machined, the obtained secondary molded product is obtained. It is described that deformation is likely to occur.

[Recovery of hydrocarbon resources]
In addition, downholes (underground excavations) are provided for the recovery of hydrocarbon resources from geological structures that contain hydrocarbon resources such as petroleum (including shale oil) and natural gas (including shale gas). Yes. Downhole tools such as plugs are used for the formation, repair or promotion of resource recovery (Patent Documents 4 and 5). The use of degradable resin as a downhole tool or downhole tool member (referred to as a member of a downhole tool) can be disintegrated in the downhole without being collected on the ground after use. Is expected.

That is, downhole tools and downhole tool members (hereinafter sometimes referred to as “downhole tools or their members”) used for the recovery of hydrocarbon resources are successively placed in the wells until the wells are completed. Although it is arranged, it is necessary to remove them at the stage where production of oil, natural gas or the like is started. Downhole tools and downhole tool members are usually not designed to be released and recovered after use and are often made of metal or inorganic materials, It can be removed by drilling out or by other methods such as drilling out, but it has been necessary to spend much money and time for crushing and drilling. There are also specially designed plugs (retrievable plugs) that can be recovered after use, but since the downhole tools such as plugs are located deep underground, there are many ways to recover all of them. It was expensive and time consuming. Accordingly, attempts have been made to improve the use of degradable materials as downhole tools or their members.

Patent Document 6 discloses a composition for balls that decomposes, dissolves, peels off, or significantly deteriorates in physical properties over time in the presence of hydrocarbons and formation heat. More specifically, in Patent Document 6, 65.6 ° C. (corresponding to 150 degrees Fahrenheit) placed in a sleeve slidable between a first position and a second position in the tube. A combination of a ball and a ball sheet (both corresponding to a downhole tool or a member thereof) containing a material that decomposes at a temperature exceeding 35 ° C., and a material that decomposes at a temperature exceeding 65.6 ° C. is a thermosetting polymer, It is described that it is a thermoplastic polymer, an elastomer and the like, and may further contain fibers or particles of aramid, glass, carbon, boron, polyester, cotton and ceramics.

As described above, under the growing demand for securing energy resources and protecting the environment, the mining conditions such as deepening have become increasingly severe, especially as mining of unconventional resources has expanded. The diversification of mining conditions, for example, the temperature conditions are diversifying from less than 60 ° C. to about 200 ° C. accompanying the diversification of depth and the like. That is, as a downhole tool such as plugs and balls (ball sealer) or its members, mechanical strength (such as tensile strength and compression strength) capable of transporting the material to a depth of several thousand meters, Oil resistance, water resistance and heat resistance, drilling and fracturing that maintain mechanical strength, etc. even in contact with hydrocarbon resources to be recovered under high temperature and high humidity environment in deep hole underground Therefore, when closing the downhole, various properties such as sealing performance and mechanical strength capable of maintaining the blocking even by high water pressure have been demanded. Furthermore, if the dimensional accuracy of the downhole tool or its components is insufficient, it may be necessary to perform various operations in well drilling at higher pressures, and damage or destruction of the downhole tool or its components may occur. Due to the fear, dimensional accuracy is also desired for the downhole tool or its members. In addition, at the stage where the wells for hydrocarbon resource recovery are completed, there are various environments in the temperature conditions and other conditions associated with the diversification of depth, etc., as described above. ), It is required to have a characteristic that it can be easily removed.

As a resin composition for solidification extrusion molding used to obtain a solidification extrusion resin molded product formed by solidification extrusion molding or a solidification extrusion resin secondary molded product formed by machining a solidification extrusion resin molding product Is required to have sufficient mechanical strength, formability, machinability, dimensional accuracy, and other properties. In addition, in downhole tools or their components and other applications, balanced impact resistance and decomposability are required. It has been desired to provide a solidified extrusion molding resin composition.

JP 2005-226031 A (corresponding to US Patent Application Publication No. 2008/0038517) Japanese Patent No. 4073052 (corresponding to US Pat. No. 5,908,917) JP 2010-69718 A US Patent Application Publication No. 2011/0277789 US Patent Application Publication No. 2005/0205266 US Patent Application Publication No. 2012/0181032

The object of the present invention is suitable for formation of a solidified extruded resin molded product or formation of a solidified extruded resin secondary molded product by machining, for example, a solidified extrusion suitable for uses such as a downhole tool for well drilling or a member thereof. A resin composition for molding, which has balanced mechanical properties such as impact resistance and mechanical strength, and further has a decomposability, a solidified extrusion molding resin composition, and a solidification excellent in mechanical properties, etc. The object is to provide an extruded resin molded product.

As a result of intensive studies to solve the above problems, the inventors of the present invention contain a decomposable resin, a reinforcing material, and a toughness improver in a predetermined ratio, and have an Izod impact strength (no notch) and an Izod impact strength. It was found that the mechanical properties such as (with a notch) were within a predetermined range, whereby the problem could be solved, and the present invention was completed.

That is, according to the present invention, when the total of the decomposable resin, the reinforcing material and the toughness improving agent is 100% by mass, the decomposable resin is 60 to 97% by mass, the reinforcing material is 3 to 37% by mass, and the toughness improving agent. A decomposable resin composition for solidification extrusion molding containing 0 to 3.5% by mass,
The above-described decomposable resin for solidification extrusion molding characterized by having an Izod impact strength (without notch) of 500 J / m or more, an Izod impact strength (with notch) of 50 J / m or more, and a tensile strength of 135 MPa or more. A composition is provided.

In addition, according to the present invention, as an embodiment, the following decomposable resin compositions for solidification extrusion molding are provided (1) to (6).
(1) The decomposable resin composition for solidification extrusion molding, wherein the decomposable resin is an aliphatic polyester.
(2) The said decomposable resin composition for solidification extrusion molding whose degradable resin is polyglycolic acid.
(3) The said decomposable resin composition for solidification extrusion molding in which a toughness improving agent contains a thermoplastic elastomer.
(4) The decomposable resin composition for solidification extrusion molding, wherein the thermoplastic elastomer is a thermoplastic polyester elastomer.
(5) The decomposable resin composition for solidification extrusion molding, wherein the thermoplastic polyester elastomer is a polyester / polyether block copolymer or an aromatic polyester / aliphatic polyester block copolymer.
(6) Decomposable resin 60 to 97% by mass, reinforcing material 3 to 37% by mass, toughness improver 0 to 0% when the total of degradable resin, reinforcing material, toughness improver and chain extender is 100% by mass The above decomposable resin composition for solidification extrusion molding comprising 3.5% by mass and a chain extender of 0 to 3% by mass.

Furthermore, according to the present invention, a solidified extrusion decomposable resin molded product formed by solidifying and extruding the solidified extrusion moldable decomposable resin composition, and machining the solidified extrudable resin molded product Thus, a solidified extrusion-decomposable resin secondary molded product is provided.

Furthermore, according to the present invention, there is provided a downhole tool or a member thereof formed from the above-mentioned solidified extrusion-decomposable resin molded product or solidified extrusion-decomposable resin secondary molded product, in particular, a ball sealer, a ball sheet, The downhole tool or a member thereof selected from the group consisting of a flack plug and a bridge plug is provided.

And according to this invention, the collection | recovery method of the hydrocarbon resource which uses the said downhaul tool or its member is provided.

According to the present invention, when the total of the decomposable resin, the reinforcing material and the toughness improving agent is 100% by mass, the decomposable resin is 60 to 97% by mass, the reinforcing material is 3 to 37% by mass, and the toughness improving agent is 0 to 0%. A decomposable resin composition for solidification extrusion molding containing 3.5% by mass,
The above-described decomposable resin for solidification extrusion molding characterized by having an Izod impact strength (without notch) of 500 J / m or more, an Izod impact strength (with notch) of 50 J / m or more, and a tensile strength of 135 MPa or more. By being a composition, it is suitable for the formation of solidified extruded resin molded products and the formation of solidified extruded resin secondary molded products by machining, for example, suitable for applications such as downhole tools for well drilling or its members A resin composition for extrusion molding, which has a balanced mechanical property such as impact resistance and mechanical strength, and a moldability (hereinafter simply referred to as a solid extrusion resin molded product with high dimensional accuracy if desired). It is also possible to provide a solidified extrusion molding resin composition having a “degradability” and a solidified extrusion resin molded article having excellent mechanical properties. The effect is achieved that that.

I. Decomposable resin composition for solidified extrusion molding The degradable resin composition for solidified extrusion molding of the present invention has a decomposable resin composition of 60 to 97 when the total of the decomposable resin, the reinforcing material and the toughness improver is 100% by mass. A decomposable resin composition for solidification extrusion molding containing 1% by mass, 3 to 37% by mass of a reinforcing material, and 0 to 3.5% by mass of a toughness improver, and having an Izod impact strength (no notch) of 500 J / m The above-described decomposable resin composition for solidification extrusion molding having an Izod impact strength (notched) of 50 J / m or more and a tensile strength of 135 MPa or more.

1. Degradable resin The degradable resin contained in the decomposable resin composition for solidification extrusion molding of the present invention is, for example, biodegradable that is degraded by microorganisms in soil, or more desirable by a solvent, particularly water. There is a degradable resin having hydrolyzability that is decomposed by acid or alkali, and may be a degradable resin that can be chemically decomposed by some other method, for example, under heating conditions of a predetermined temperature or higher. Preferably, it is a hydrolyzable resin that decomposes with water at a predetermined temperature or higher. As a result of the brittleness of the resin due to a decrease in the degree of polymerization or the like, the resin easily collapses and loses its shape by applying a very small mechanical force (hereinafter sometimes referred to as “disintegration”). ) Resin is also a degradable resin.

The decomposable resin composition for solidification extrusion molding of the present invention is a decomposable resin composition suitable for molding by solidification extrusion molding, and further a secondary molded product by machining, particularly a downhole tool for well drilling. Alternatively, from the viewpoint of being a decomposable resin composition for solidification extrusion molding suitable for molding of the member, examples of the decomposable resin include polylactic acid (PLA), polyglycolic acid (PGA), poly-ε-caprolactone (PCL). ) And the like, and polyvinyl alcohol (such as partially saponified polyvinyl alcohol having a degree of saponification of about 80 to 95 mol%), and the like, preferably aliphatic polyester. Moreover, as long as the property as a degradable resin is not lost, it can also be used combining the component which forms aromatic polyesters, such as terephthalic acid. Decomposable resins can be used alone or in combination of two or more by blending or the like.

From the viewpoint of solidification extrusion moldability, moldability of the secondary molded product by machining, and degradability, the aliphatic polyester is at least one selected from the group consisting of PGA, PLA and glycolic acid / lactic acid copolymer (PGLA). More preferably, it is a seed, and PGA is even more preferable. That is, most preferred is a decomposable resin composition for solidification extrusion molding in which the degradable resin is PGA. As PGA, in addition to the homopolymer of glycolic acid, the glycolic acid repeating unit is 50% by mass or more, preferably 75% by mass or more, more preferably 85% by mass or more, and still more preferably 90% by mass or more. It includes 95% by mass or more, most preferably 99% by mass or more, and particularly preferably 99.5% by mass or more of a copolymer. As PLA, in addition to a homopolymer of L-lactic acid or D-lactic acid, a repeating unit of L-lactic acid or D-lactic acid is 50% by mass or more, preferably 75% by mass or more, more preferably 85% by mass. More preferably, a copolymer having 90% by mass or more, and further, by mixing poly-L-lactic acid and poly-D-lactic acid, each molecular chain is suitably entangled to form a stereocomplex. And a stereocomplex type polylactic acid known to have improved heat resistance. As PGLA, the ratio (mass ratio) of glycolic acid repeating units to lactic acid repeating units is 99: 1 to 1:99, preferably 90:10 to 10:90, more preferably 80:20 to 20:80. Copolymers can be used.

The content of the decomposable resin in the decomposable resin composition for solidification extrusion molding of the present invention is a solidified extrusion decomposable resin molded product formed by solidifying and extruding the decomposable resin composition for solidification extrusion molding, or Solidified extrusion-decomposable resin secondary molded product formed by machining the solidified extrusion-decomposable resin molded product (hereinafter sometimes collectively referred to as “solidified extrusion-decomposable resin molded product or secondary molded product”) ), In particular, taking into account the mechanical properties and decomposability required for each downhole tool for well drilling or its members, for example, ease of removal from the well as required. be able to. Specifically, when the total of the decomposable resin, the reinforcing material and the toughness improver is 100% by mass, it is usually 60 to 97% by mass, preferably 62 to 95% by mass, more preferably 64 to 93% by mass. Depending on the combination with the reinforcing material and toughness improving agent described later, it is in the range of 65 to 90% by mass, and further 66 to 88% by mass.

2. Reinforcing Material The decomposable resin composition for solidification extrusion molding of the present invention can have balanced mechanical properties and degradability by containing a reinforcing material in a predetermined ratio together with the decomposable resin, and as a result, The solidified extrusion-decomposable resin molded product or the secondary molded product, in particular, the downhole tool or a member thereof can have mechanical properties and degradability required for each. As the reinforcing material contained in the decomposable resin composition for solidified extrusion molding according to the present invention, materials conventionally used as reinforcing materials or fillers in the resin composition for solidified extrusion molding can be used. That is, as the reinforcing material, a fibrous reinforcing material or a granular or powdery reinforcing material can be used, but from the viewpoint of solidification extrusion moldability, formability of a secondary molded product by machining, and decomposability, Fibrous reinforcement is preferred.

Examples of fibrous reinforcing materials include glass fibers, carbon fibers, asbestos fibers, silica fibers, alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, potassium titanate fibers, and the like; stainless steel, aluminum Metal fibrous materials such as titanium, steel and brass; high melting point organic fibrous materials such as polyamide, fluororesin, polyester resin and acrylic resin; and the like. As the fibrous reinforcing material, short fibers having a length of 10 mm or less, preferably 1 to 6 mm, more preferably 1.5 to 4 mm are preferable, inorganic short fibers are more preferably used, and glass fibers are particularly preferable. . The fibrous reinforcing material, particularly glass fiber, is preferably preliminarily dried. By reducing the moisture content of the fibrous reinforcing material to 100 ppm or less, preferably 50 ppm or less by drying treatment, the moisture content in the decomposable resin composition for solidification extrusion molding is reduced, and the decomposition of the decomposable resin is suppressed. In addition, the adhesion between the fibrous reinforcing material and the degradable resin can be improved, and the effect of adding the reinforcing material can be improved. The drying condition of the fibrous reinforcing material is usually 18 to 28 hours at a temperature of 70 to 130 ° C., and preferably 20 to 24 hours at a temperature of 80 to 120 ° C.

Granular or powdery reinforcing materials include mica, silica, talc, alumina, kaolin, calcium sulfate, calcium carbonate, titanium oxide, ferrite, clay, glass powder (milled fiber, etc.), zinc oxide, nickel carbonate, iron oxide, quartz Examples thereof include powder, magnesium carbonate, and barium sulfate. The particle-like or powder-like reinforcing material has a particle size of usually 0.01 to 1000 μm, preferably 0.05 to 500 μm, more preferably 0.1 to 200 μm. Among these, milled fiber (sometimes referred to as milled glass fiber) is a reinforcing material having a powdery or cotton-like appearance obtained by pulverizing glass fiber to a size of 6 to 11 μm in length and 30 to 150 μm in length. When the decomposable resin composition for solidification extrusion molding is solidified and extrusion molded, cracking or the like may occur in the glass fiber due to stress concentration, but the effect of suppressing this may be obtained.

These reinforcing materials can be used alone or in combination of two or more. The reinforcing material may be treated with a sizing agent or a surface treatment agent as necessary. Examples of the sizing agent or surface treating agent include functional compounds such as epoxy compounds, isocyanate compounds, silane compounds, and titanate compounds. These compounds may be used after being subjected to surface treatment or focusing treatment on the reinforcing material in advance, or may be added simultaneously with the preparation of the resin composition. The reinforcing material subjected to the surface treatment or the bundling treatment, particularly the fibrous reinforcing material, may be further subjected to a drying treatment to reduce the moisture content. When the sizing agent or surface treatment agent absorbs moisture, the bonding surface between the reinforcing material and the decomposable resin may be decomposed during melt-kneading with the decomposable resin, and the strength may decrease due to a decrease in the interaction. The material is preferably pre-dried to remove as much water as possible. The conditions for the drying treatment can be the same as described above, but depending on the type of sizing agent, it may be thermally decomposed, so it is necessary to adjust so that the drying temperature is not too high.

The content of the reinforcing material in the decomposable resin composition for solidified extrusion molding according to the present invention is such that the mechanical properties required for the solidified extrusion decomposable resin molded product or the secondary molded product, particularly the downhole tool or its member, respectively. Degradability, for example, it can be determined as appropriate in consideration of easiness of removal from the well as required. Specifically, when the total of the decomposable resin, the reinforcing material and the toughness improving agent is 100% by mass, it is usually 3 to 37% by mass, preferably 5 to 36% by mass, more preferably 7 to 35% by mass. Depending on the combination with the toughness improving agent described later, it is in the range of 8 to 34% by mass, further 9 to 33% by mass.

3. Toughness improver The decomposable resin composition for solidification extrusion molding of the present invention preferably contains a toughness improver in addition to the decomposable resin and the reinforcing material. The decomposable resin composition for solidification extrusion molding of the present invention, when containing a toughness improver together with a decomposable resin and a reinforcing material, is superior in having more balanced mechanical properties and moldability as well as degradability. It also has a high toughness. As a result, stress concentration is relaxed when solidifying and extruding the decomposable resin composition for solidification extrusion molding, and central whitening (centerline porosity) and cracking due to stress concentration can be suppressed. A solidified extrusion-decomposable resin molded product having a large thickness can be obtained with high dimensional accuracy. Further, the obtained solidified extrusion decomposable resin molded product or secondary molded product, and the downhole tool or its member formed from the molded product or secondary molded product have the required mechanical characteristics and degradability. For example, it can have high impact resistance which is difficult to be damaged even if it contacts or collides with various members used for well excavation.

Further, when the decomposable resin composition for solidification extrusion molding of the present invention contains a toughness improver together with the decomposable resin and the reinforcing material, when the solidification extrusion molding of the decomposable resin composition for solidification extrusion molding is performed, the reinforcing material It was found that the effect of suppressing the occurrence of cracks and the like due to stress concentration on the surface was obtained, and the dimensional accuracy of the molded product and the secondary molded product was good. The reason for this is not clear, but as a result of containing a toughness improver, the melting characteristics of the decomposable resin composition for solidification extrusion change, and the fluidity of the resin material during solidification extrusion improves. It is presumed that the dimensional accuracy of the secondary molded product is increased by reducing the residual stress of the formed extrusion-decomposable resin molded product. Since the fluidity of the resin material during solidification extrusion molding is improved, there is a possibility that the back pressure can be reduced or the molding temperature can be lowered in solidification extrusion molding. In addition, for example, the downhole tool or its member formed from the molded product or the secondary molded product does not need to perform various operations in the well drilling at a higher pressure, and the downhole tool or its member is not damaged. It has been found that it contributes to cost reduction and process shortening of well drilling because there is little possibility of destruction.

As the toughness improver contained in the decomposable resin composition for solidified extrusion molding of the present invention, by improving the toughness of the decomposable resin composition, balanced mechanical properties, specifically, Izod impact Provided a decomposable resin composition for solidified extrusion molding having a strength (without notch) of 500 J / m or more, an Izod impact strength (with notch) of 50 J / m or more, and a tensile strength of 135 MPa or more and excellent moldability. As long as it can be used, the composition (type / material) and form thereof are not particularly limited. For example, the form of the toughness improver includes a granular toughness improver and / or a fibrous toughness improver, and their shape and size (particle size, particle size distribution, fiber diameter, fiber length, etc.) are It can be selected appropriately.

As the composition of the toughness improver, first, materials having elasticity, for example, various rubber materials or elastomer materials can be mentioned. Specifically, natural rubber or isoprene rubber, ethylene propylene rubber, butyl rubber, styrene butadiene rubber, acrylic rubber, aliphatic polyester rubber, chloroprene rubber, polyurethane rubber, or other natural rubber or synthetic rubber; thermoplastic olefin elastomer (ethylene Propylene copolymer, ethylene / vinyl acetate copolymer, etc.), thermoplastic polyester elastomer (aromatic polyester / aliphatic polyester block copolymer, polyester / polyether block copolymer, etc.), thermoplastic polyurethane elastomer, styrene / butadiene / styrene block Copolymers, styrene thermoplastic elastomers such as styrene / ethylene / butylene / styrene block copolymer (SEBS), rubber, etc. in the hard component phase of methacrylate resins Thermoplastic elastomers of the multilayer structure polymer and the like containing the soft component phase; and the like. Furthermore, biodegradable, hydrolyzable, or degradable rubber materials or elastomer materials that can be chemically decomposed by some other method are preferable, such as aliphatic polyester rubber, polyurethane rubber, natural rubber, isoprene rubber, etc. In addition, a rubber material or an elastomer material having a hydrolyzable functional group can be used. Further, depending on the combination with the reinforcing material or application, so-called adhesive components such as polar group-modified polyolefins (Modic (registered trademark), etc.), glycidyl methacrylate / ethylene copolymers (bond first (registered trademark), etc.) and ethylene -A vinyl acetate copolymer etc. can be mentioned.

[Thermoplastic elastomer]
As the toughness improver, solidified extrusion-decomposable resin molded product or secondary molded product, more specifically, balanced mechanical properties and moldability and decomposability due to the toughness improving effect of downhole tool or its members In view of the above, and from the viewpoint of ease of disposal and recovery, etc., a thermoplastic elastomer is preferable, and a thermoplastic polyester elastomer is more preferable.

As the thermoplastic polyester elastomer, a block copolymer containing an aromatic polyester unit such as polybutylene terephthalate as a hard segment and an aliphatic polyether unit as a soft segment, that is, a polyester / polyether block copolymer and a soft segment Examples of the block copolymer include an aliphatic polyester unit, that is, an aromatic polyester / aliphatic polyester block copolymer, and a polyester / polyether block copolymer is more preferable.

[Other degradable resins]
Other degradable resins can also be used as toughness improvers. That is, it is the main part of the decomposable resin composition for solidification extrusion molding of the present invention, preferably in the range of 60 to 97% by mass (the total of the decomposable resin, the reinforcing material and the toughness improving agent is 100% by mass). A decomposable resin different from the decomposable resin contained in can be contained as a toughness improver. For example, by adding PLA as a toughness improving agent as a degradable resin to PGA, which is a preferable degradable resin, the effect of improving toughness can be realized, and balanced mechanical characteristics and molding are achieved. The ability to further improve the properties and degradability.

[Toughness improver form]
Further, from the viewpoint of improving the toughness of the decomposable resin and uniform dispersibility, the form and shape of the toughness improving agent in the decomposable resin composition for solidification extrusion molding is preferably particulate, especially spherical. The particle size (meaning the average particle size of 100 particles measured by electron microscope observation of the cross section) is preferably 1 nm to 10 μm, more preferably 5 nm to 5 μm, and more preferably 10 nm to More preferably, it is 2 μm.

[Content of toughness improver]
The content of the toughness-improving agent in the decomposable resin composition for solidification extrusion molding of the present invention is the mechanical properties required for the solidification extrusion decomposable resin molded product or secondary molded product, particularly the downhole tool or its member, respectively. In addition, it can be appropriately determined in consideration of formability and decomposability, for example, ease of removal from the well as required. Specifically, when the total of the decomposable resin, the reinforcing material and the toughness improver is 100% by mass, it is usually 0 to 3.5% by mass, preferably 0 to 3.4% by mass, more preferably 0 to 3.3% by mass, depending on the combination of the degradable resin and the reinforcing material described above, in the range of 0.1 to 3.2% by mass, and further 0.2 to 3.1% by mass. is there. In addition, the content of the toughness improving agent of 0% by mass means that the decomposable resin composition for solidification extrusion molding does not contain the toughness improving agent.

4). Other compounding components The decomposable resin composition for solidified extrusion molding of the present invention contains a degradable resin and a reinforcing material, preferably further containing a toughness improver in a predetermined ratio, so that balanced mechanical properties and moldability are obtained. As long as they do not impair the object of the present invention, other compounding ingredients include chain extenders, stabilizers, degradation accelerators or degradation inhibitors, lubricants, mold corrosion inhibitors, processing Various additives such as a property improving agent and a colorant, and other resin materials can be contained. For example, when the decomposable resin composition for solidification extrusion molding contains a chain extender, the molecular weight of the decomposable resin increases, and impact resistance, specifically, Izod impact strength (no notch) and Izod Since impact strength (with a notch) improves further, it is preferable.

(Chain extender)
As the chain extender contained in the decomposable resin composition for solidification extrusion molding of the present invention, compounds conventionally used as the chain extender of degradable resins can be used, such as oxazoline compounds and isocyanates. Compounds, carbodiimide compounds, carbodiimide-modified isocyanate compounds, fatty acid bisamide compounds, alkyl-substituted fatty acid monoamide compounds, 1- to 3-functional glycidyl-modified compounds having a triazine skeleton, epoxy compounds, acid anhydrides, oxazine compounds, ketene compounds, etc. These 1 type (s) or 2 or more types can be contained in combination. Oxazoline compounds and isocyanate compounds are preferred from the viewpoint of improving mechanical properties due to the effect of improving impact resistance and improving balance of degradability.

Examples of the oxazoline compound include compounds having two or more oxazoline rings in the molecule, such as 2,2′-m-phenylene-bis- (2-oxazoline) [1,3-PBO: “2,2 ′-(1 , 3-phenylene) bis (2-oxazoline) ". 2,2′-bis- (2-oxazoline), 2,2′-methylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (2-oxazoline), 2,2′- Trimethylene-bis- (2-oxazoline), 2,2'-tetramethylene-bis- (2-oxazoline), 2,2'-hexamethylene-bis- (2-oxazoline), 2,2'-octamethylene- Bis- (2-oxazoline), 2,2′-ethylene-bis- (4,4′-dimethyl-2-oxazoline), 2,2′-p-phenylene-bis- (2-oxazoline), 2,2 2,2'-bis- (2-oxazoline) compounds such as' -m-phenylene-bis- (4,4'-dimethyl-2-oxazoline); bis- (2-oxazolinylcyclohexane) sulfide, bis- (2-Oki Sledding sulfonyl norbornane) sulfide, include such molecular chain terminal or side chain of two or more polymer compounds oxazoline ring structure is introduced, 1, 3-PBO is particularly preferably used. Isocyanate compounds include aromatic diisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter), aliphatic diisocyanates having 2 to 18 carbon atoms, alicyclic diisocyanates having 4 to 15 carbon atoms, carbon numbers 8 to 15 araliphatic diisocyanates, modified products of these diisocyanates, and mixtures of two or more thereof can be used. Specific examples of the isocyanate include phenylene diisocyanate, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthylene diisocyanate, ethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), Examples include lysine triisocyanate, and xylylene diisocyanate (XDI) is particularly preferably used.

The content of the chain extender in the decomposable resin composition for solidification extrusion molding of the present invention is such that the mechanical properties required for the solidification extrusion decomposable resin molded product or secondary molded product, particularly the downhole tool or its member, respectively. Or degradability, for example, it can be determined appropriately taking into account the ease of removal from the wells, etc., if necessary, but usually the total of degradable resin, reinforcing material, toughness improver and chain extender Solidified extrusion containing decomposable resin 60 to 97% by mass, reinforcing material 3 to 37% by mass, toughness improver 0 to 3.5% by mass, and chain extender 0 to 3% by mass when 100% by mass A degradable resin composition for molding is used. That is, the content of the chain extender is usually 0 to 3% by mass, preferably 0 to 2% when the total of the degradable resin, the reinforcing material, the toughness improver and the chain extender is 100% by mass. It is 8% by mass, more preferably 0 to 2.5% by mass. The content of the chain extender of 0% by mass means that the decomposable resin composition for solidification extrusion molding does not contain a chain extender.

5. Mechanical properties of decomposable resin composition for solidification extrusion molding The decomposable resin composition for solidification extrusion molding of the present invention contains a predetermined amount of a decomposable resin, a reinforcing material and a toughness improver, and optionally a chain extender. The Izod impact strength (without notch) is 500 J / m or more, the Izod impact strength (with notch) is 50 J / m or more, and the tensile strength is 135 MPa or more. This is a resin composition for solid extrusion molding that is suitable for forming a molded product or forming a solid extrusion-decomposable resin secondary molded product by machining, for example, a downhole tool for drilling a well or its member. Thus, it is possible to provide a solidified extrusion molding resin composition having balanced mechanical properties such as impact resistance and mechanical strength, and further having degradability.

[Izod impact strength (no notch)]
The decomposable resin composition for solidified extrusion molding of the present invention has an Izod impact strength (no notch) of 500 J / m or more. The Izod impact strength (no notch) of the decomposable resin composition for solidification extrusion molding is measured as follows for an unnotched test piece in accordance with ASTM D256 (corresponding to ISO 180). That is, using an injection molding machine having a uniaxial full flight screw, if the decomposable resin is crystalline, heat it above its melting point and mold and cool it with a mold set at a temperature near the crystallization temperature. Thus, a rectangular parallelepiped test piece (no notch) having a length of 63.5 mm, a width of 12.7 mm, and a thickness of 3.0 mm as defined in ASTM D256 is prepared. When the decomposable resin is amorphous, the test piece having the above-mentioned shape is prepared by heating above its glass transition temperature and molding and cooling with a mold set at a temperature below the glass transition temperature. In either case, the gate is the end of the specimen in the longitudinal direction. About the prepared test piece, the Izod impact strength calculated by measuring the impact energy absorbed at the time of breaking the notched test piece at room temperature (temperature 23 ° C. ± 1 ° C.) using a pendulum type impact tester ( The average value of n = 5 (unit: J / m) is defined as the Izod impact strength (no notch) of the decomposable resin composition for solidification extrusion molding.

If the Izod impact strength (no notch) is less than 500 J / m, the solidified extrusion decomposable resin molded product or the solidified extrudable resin formed by solidification extrusion molding of the solidification extrusion molding decomposable resin composition Solid extrusion-decomposable resin secondary molded product formed by machining the molded product (hereinafter sometimes referred to as “solidified extrusion-decomposable resin molded product or secondary molded product”), for example, solidified extrusion-decomposable resin There is a possibility that the impact resistance of the downhole tool or its member which is a molded product or a secondary molded product is insufficient. That is, for example, i) a downhole tool such as a ball or its member is broken or a scratch (notch) occurs during movement at high speed, or ii) a ball seat (downhole tool) during movement of the ball The ball is broken when it is impacted by another member when it is set on the member). At that time, if a notch is generated in i), the impact strength at this stage is greater than the impact strength without the notch. As a result of the impact strength with a significantly smaller notch, it is more likely to break. Or iii) When the ball is set on the ball sheet and pressure is applied, the ball may be crushed or broken by the pressure due to scratches or chips. The Izod impact strength (no notch) of the decomposable resin composition for solidification extrusion molding is preferably 550 J / m or more, more preferably 600 J / m or more. Although there is no upper limit value for Izod impact strength (no notch), it is generally 4000 J / m or less.

[Izod impact strength (notched)]
Moreover, the decomposable resin composition for solidification extrusion molding of the present invention has an Izod impact strength (notched) of 50 J / m or more. The Izod impact strength (with notch) of the decomposable resin composition for solidification extrusion molding is measured for a test piece with a notch. That is, a rectangular parallelepiped test piece (notched) having a length of 63.5 mm, a width of 12.7 mm, and a thickness of 3.0 mm prepared according to ASTM D256 by the method described in detail for the Izod impact strength (without notch). ), The Izod impact strength (n = 5) calculated by measuring the impact energy absorbed at the time of fracture of the notched specimen at room temperature (temperature 23 ° C. ± 1 ° C.) using a pendulum impact tester The average value (unit: J / m) is the Izod impact strength (with notch) of the decomposable resin composition for solidified extrusion molding. When the Izod impact strength (with notch) is less than 50 J / m, the balance with the previously described Izod impact strength (without notch) is poor, and the solidified extrusion-decomposable resin molded product or secondary molded product, for example, The impact resistance of the downhole tool or its members may be insufficient. The Izod impact strength (with a notch) of the decomposable resin composition for solidification extrusion molding is preferably 55 J / m or more, and more preferably 60 J / m or more. Although there is no upper limit value for Izod impact strength (notched), it is generally 400 J / m or less.

As described above, the decomposable resin composition for solidified extrusion molding according to the present invention generally has an Izod impact strength (with notch) magnitude of 1/12 or more, preferably with respect to the Izod impact strength (without notch) magnitude. Is 1/10 or more. As a result, in the solidified extrusion decomposable resin molded product or secondary molded product of the present invention, and further in the downhole tool or the member formed from the solidified extrudable resin molded product or secondary molded product, there are some circumstances. Even if scratches or damage occur, it has an excellent property that it is not easily affected by an increase in impact due to the shape of the scratch or damaged portion, and the impact resistance is hardly lowered. The magnitude of the Izod impact strength (with notch) relative to the magnitude of the Izod impact strength (without notch) is not particularly limited, but is usually 1/3 or less, and in most cases 1/4 or less.

[Tensile strength]
Furthermore, the decomposable resin composition for solidified extrusion molding of the present invention has a tensile strength of 135 MPa or more. The tensile strength of the decomposable resin composition for solidified extrusion can be measured according to JIS K7113. That is, for a test piece (No. 1 test piece) having a shape defined in JIS K7113 prepared by injection molding under the same conditions as the preparation of the test piece used for measurement of impact strength, normal temperature (temperature 23 ° C.). (± 1 ° C.), a tensile test is performed at a speed of 50 mm / min, and the tensile stress when the test piece breaks is measured and calculated (average value of n = 5, unit: MPa). If the tensile strength of the decomposable resin composition for solidification extrusion molding is less than 135 MPa, the mechanical strength required for the solidification extrusion decomposable resin molded product or secondary molded product, for example, a downhole tool or a member thereof may be insufficient. is there. The tensile strength of the decomposable resin composition for solidification extrusion molding is preferably 140 to 300 MPa, more preferably 145 to 270 MPa, and particularly preferably 150 to 250 MPa from the viewpoint of the above-described functional expression.

[Tensile elongation]
Still further, the decomposable resin composition for solidification extrusion molding of the present invention preferably has a tensile elongation of 3% or more. The tensile elongation of the decomposable resin composition for solidified extrusion can be measured according to JIS K7113. That is, a test piece (No. 1 test piece) prepared in accordance with the provisions of JIS K7113 by the method described in detail with respect to the tensile strength previously, is pulled at a speed of 50 mm / min at room temperature (temperature 23 ° C. ± 1 ° C.). The test is performed and the elongation when the test piece is broken is measured and calculated (average value of n = 5, unit:%). If the tensile elongation of the decomposable resin composition for solidification extrusion molding is less than 3%, the toughness of the solidification extrusion decomposable resin molded product or secondary molded product, for example, the downhole tool or its member, is insufficient. There is a risk of crushing or breaking or chipping during operation. The tensile elongation of the decomposable resin composition for solidification extrusion molding is preferably 3.4% or more, more preferably 3.7% or more, and still more preferably 4% or more. There is no particular upper limit on the tensile elongation, but it is generally 30% or less.

6). Manufacturing method of decomposable resin composition for solidification extrusion molding The manufacturing method of the decomposable resin composition for solidification extrusion molding of this invention is not specifically limited. That is, if other compounding components such as a degradable resin, a reinforcing material and a toughness improver, and a chain extender to be included if desired are blended at once or sequentially according to a conventional method, a uniformly dispersed mixed state is obtained. Good.

II. Solidified extrusion-decomposable resin molded product The solidified extrusion-decomposable resin molded product of the present invention can be formed by solid-extrusion molding the degradable resin composition for solidified extrusion molding of the present invention. As explained above, solidification extrusion molding is a molding in which a resin material is melted and extruded from a heating shaping mold, and then cooled and solidified in a cooling shaping mold while a high back pressure during extrusion is applied to the resin material. Unlike so-called extrusion molding, it is a distinct molding method.

(Solidified extrusion)
The solidification extrusion molding method for forming the solidified extrusion decomposable resin molded product of the present invention is not particularly limited as long as the solidified extrusion decomposable resin molded product can be formed from the degradable resin composition for solidified extrusion molding of the present invention. It is not limited, For example, the shaping | molding method containing the following processes is employable.

That is, a decomposable resin composition for solidification extrusion molding containing a predetermined amount of other compounding components such as a decomposable resin, a reinforcing material and a toughness improver, and a chain extender to be contained as required is supplied to an extruder, Melt-kneading step 1 with
A flow path having a cross-sectional shape of the extrudate formed by communicating the decomposable resin composition for solidification extrusion molding melted by melt kneading from the extrusion die at the tip of the extruder, and a cooling means; Extruding into a flow path of a forming die comprising:
Step 3 of cooling the molten extrudate in the flow path of the forming die below the melting point of the decomposable resin to solidify, and then extruding the solidified extrudate from the tip of the forming die;
Step 4 of pressurizing the solidified extrudate and taking it out while applying back pressure in the forming die direction to obtain a solidified extrudable resin molded product; and, if desired,
The solidification extrusion molding method including the step 5 of heat-treating at a temperature below the melting point of the decomposable resin can be employed.

[Shape and size of solidified extrusion-decomposable resin molded product]
The shape and size of the solidified extrusion decomposable resin molded product formed by solidifying and extruding the decomposable resin composition for solidified extrusion molding according to the present invention are selected according to the application and are not particularly limited. . For example, a round bar having a predetermined diameter, a flat plate having a predetermined thickness, a pipe having a predetermined diameter and thickness, and a modified cross-sectional shape, etc. By appropriately selecting the size, a solidified extrudable resin molded product having a desired shape and size can be obtained. The shape is preferably a round bar or a flat plate, more preferably a round bar, because it is often suitable for a material for machining such as cutting described later. The diameter or thickness of the solidified extrusion-decomposable resin molded product is usually 5 mm or more, and can be 10 mm or more, 30 mm or more, or 50 mm or more as desired. It can be 150 mm or more. If the thickness and diameter of the solidified extrudable resin molded product are too small, it may be difficult to form a solidified extrudable resin secondary molded product having a desired shape and size by machining such as cutting. On the other hand, if the thickness or diameter of the solidified extrudable resin molded product is too large, the residual stress tends to increase, and the solidified extrudable resin secondary molded product cannot be formed by machining, or the secondary molded product May be deformed.

[Mechanical properties of solidified extrusion-decomposable resin molded product]
The solidified extrusion decomposable resin molded article of the present invention is formed by solidifying and extruding the decomposable resin composition for solidified extrusion molding of the present invention having specific impact strength, tensile strength, etc. Has excellent mechanical properties. When the decomposable resin composition for solid extrusion molding is solidified and extrusion molded, generally, the mechanical properties tend to be lower than that of the decomposable resin composition for solid extrusion molding. Has an Izod impact strength (without notch) of 150 J / m or more, preferably 180 J / m or more, more preferably 200 J / m or more, and an Izod impact strength (with notch) of 30 J / m or more, preferably 35 J. / M or more, more preferably 40 J / m or more, and a tensile mechanical strength of 60 MPa or more, preferably 70 MPa or more, more preferably 80 MPa or more, having balanced mechanical properties. In addition, as a sample used for measuring the Izod impact strength (without notch and with notch) of the solidified extrusion decomposable resin molded product and the tensile strength, the decomposable resin composition for solidified extrusion molding was solidified and extruded, and the temperature was measured. After heat treatment at 170 ° C. for 8 hours, cutting from the solidified extrudable resin molded product within one month of storage at room temperature in the MD direction (longitudinal direction) or TD direction (perpendicular to the longitudinal direction) A test piece prepared by cutting into the above dimensions and shape by processing is used.

[Use]
The solidified extrusion-decomposable resin molded product of the present invention can be used in a desired application with the shape and size formed by solidified extrusion molding or by cutting into a required length or thickness. The application is not particularly limited. Depending on the application, the solidified extrusion-decomposable resin molded product of the present invention and other members can be used in combination. Moreover, it can use especially preferably for the use of the raw material for machining for forming the solidification extrusion decomposable resin secondary molded product of desired shape and magnitude | size by machining, such as cutting mentioned later. Moreover, it can use preferably also for the use of the various members used for the downhaul used for excavation of hydrocarbon resources, such as oil and gas, ie, the downhaul tool or downhaul tool member which are explained in full detail behind.

III. Solidified Extrudable Resin Secondary Molded Product Solidified Extrudable Resin Molded Product of the Present Invention By Machining the Solidified Extrudable Resin Molded Product Formed by Solidified Extrusion Forming of the Degradable Resin Composition for Solidified Extrusion Molding of the Present Invention A decomposable resin secondary molded product can be formed. That is, by using the solidified extrusion decomposable resin molded product formed by solidification extrusion molding of the solidified extrusion molding composition of the present invention as a machining material, by machining the machining material, A solidified extrusion-decomposable resin secondary molded product can be formed.

〔Machining〕
In order to form the solid extrusion-decomposable resin secondary molded product of the present invention, machining performed on the material for machining is not particularly limited, and machining such as cutting, drilling and cutting, and combinations thereof are possible. It is representative. Examples of the cutting include turning using a single blade tool, grinding, planing, and boring. Cutting methods using multiple blades include milling, threading, gear cutting, sculpting, file processing, etc., and may include drilling. Examples of the cutting process include cutting with a blade (saw), cutting with abrasive grains, and cutting by heating and melting. In addition, special processing methods such as grinding, plastic working such as punching using a knife-like tool and scribing, laser processing, and the like can also be applied.

When the solidified extrusion-decomposable resin molded product, which is a material for machining, has a shape of a large flat plate or round bar, generally, the solidified extrusion-decomposable resin molded product is cut into an appropriate size or thickness, Grind the cut solidified extrusion decomposable resin molded product into a desired shape, drill holes in the required locations, and finish as necessary. Can be formed. The order of machining is not limited to this. When the solidified extrusion-decomposable resin molded product, which is a material for machining, melts due to frictional heat during machining, it is desirable to perform machining while cooling the cutting surface or the like. If the material for machining is excessively heated by frictional heat, it causes deformation and coloring. Therefore, the solidified extrusion-decomposable resin molded product or processed surface that is the material for machining is preferably 200 ° C. or less, more preferably 150 ° C. It is preferable to control to the following temperature.

〔shape〕
As long as the shape of the solidified extrudable resin secondary molded product of the present invention can be formed by machining the material for machining using the solidified extrudable resin molded product as a material for machining. There is no particular limitation. For example, a rod-like body having an annular or non-annular step or projection, a rod-like body having an annular or non-annular recess, or annular formed by machining a round bar-shaped solidified extrusion-decomposable resin molded product Or it can be set as the solid extrusion extrudable resin secondary molded product of shapes, such as a rod-shaped body which has a non-annular flange. Moreover, it can be set as the solid-extrusion decomposable resin secondary molded product of the shape of a ball | bowl formed by machining the solid extrusion-decomposable resin molded product of a round bar shape. It can be set as the solidification extrusion decomposable resin secondary molded article which has an annular or non-annular flange formed by machining a pipe-shaped solid extrusion extrudable resin molding.

[Mechanical properties of solidified extrusion-decomposable resin secondary molded product]
The solidified extrusion decomposable resin secondary molded article of the present invention is formed by solidification extrusion decomposability formed by solidifying and extruding the decomposable resin composition for solidified extrusion molding of the present invention having specific impact strength, tensile strength and the like. By being formed by machining a resin molded product, it has excellent mechanical properties. When the decomposable resin composition for solidification extrusion molding is solidified extrusion molding and further machined, generally, the mechanical properties tend to be lower than that of the decomposable resin composition for solidification extrusion molding. The solid extrusion-decomposable resin secondary molded product of the present invention has an Izod impact strength (no notch) of 150 J / m or more, preferably 180 J / m or more, more preferably 200 J / m or more. Notched) is 30 J / m or more, preferably 35 J / m or more, more preferably 40 J / m or more, and the tensile strength is 60 MPa or more, preferably 70 MPa or more, more preferably 80 MPa or more. It has mechanical properties. In addition, as a sample used to measure the Izod impact strength (without notch and with notch) of the solidified extrusion decomposable resin secondary molded product and the tensile strength, the decomposable resin composition for solidified extrusion molding was solidified and extrusion molded. For a solidified extrudable decomposable fat secondary molded product formed by machining a solidified extrudable resin molded product that has been heat treated at 170 ° C. for 8 hours and then stored at room temperature within 1 month, MD direction or TD In the direction, a test piece prepared by cutting into the above-described size and shape by cutting is used.

[Use]
The application of the solid extrusion-decomposable resin secondary molded article of the present invention is not limited, but particularly preferred is a hydrocarbon such as petroleum (including shale oil) and gas (including shale gas). Examples include various members used for downholes used for excavation of resources, that is, a downhole tool or a downhole tool member described in detail later.

The solid extrusion-decomposable resin secondary molded product of the present invention is also used for other purposes. For example, in the electric and electronic field, wafer carrier, wafer cassette, spin chuck, tote bin, wafer boat, IC chip tray, IC chip carrier, IC transfer tube, IC test socket, burn-in socket, pin grid array socket, quad flat package, lead Examples include less chips carriers, dual in-line packages, small outline packages, reel packing, various cases, storage trays, transport device parts, and magnetic card readers.

In the field of OA equipment, various roll members in image forming apparatuses such as electrophotographic copying machines and electrostatic recording apparatuses, transfer drums for recording apparatuses, printed circuit board cassettes, bushes, paper and bill transport parts, paper feed rails, font cartridges, Ink ribbon canisters, guide pins, trays, rollers, gears, sprockets, computer housings, modem housings, monitor housings, CD-ROM housings, printer housings, connectors, computer slots, and the like.

In the field of communication equipment, mobile phone parts, pagers, various sliding materials, etc. are listed. In the automotive field, interior materials, under hoods, electronic / electric equipment housings, gas tank caps, fuel filters, fuel line connectors, fuel line clips, fuel tanks, equipment beads, door handles, various parts and the like can be mentioned. In other fields, electric wire supports, radio wave absorbers, flooring materials, pallets, shoe soles, brushes, blower fans, planar heating elements, polyswitches, and the like can be given.

IV. Downhole tool or downhole tool member As described above, the preferred use of the solidified extrudable resin molded product or secondary molded product is to use a downhole tool or downhole tool member for downhole drilling (downhole tool or That member). That is, the downhole tool or its member formed from the solidified extrusion decomposable resin molded product or secondary molded product of the present invention is derived from the degradable resin composition for solidified extrusion molding of the present invention, thereby increasing the depth. Under the harsh and diverse mining conditions, etc., it has impact resistance and decomposability against contact and collision with various members used for well drilling, contributing to cost reduction and process shortening of well drilling be able to. Therefore, the downhole tool or its member of the present invention can be preferably used in a hydrocarbon resource recovery method.

The downhole tool or member thereof derived from the decomposable resin composition for solidification extrusion molding of the present invention includes a downhole tool for well excavation used in a method for recovering hydrocarbon resources or a member thereof, particularly It is not limited. For example, plugs for drilling wells (flac plugs or bridge plugs, etc.); sleeves (flux leaves, etc.); members provided for the plugs, such as mandrels, rings, slips or wedges; mandrels, rings, slips, wedges, etc. Alternatively, elements and parts of an annular rubber member capable of expanding the diameter; a ball sealer (sometimes simply referred to as “ball”) and a ball sheet; Note that the downhole tool and the downhole tool member are relative concepts, and the boundary may not be determined strictly. For example, a ball sealer may be referred to alone as a downhole tool, or may be referred to as a downhole tool member because it is used in combination with a ball seat in a flap plug or in a sleeve.

The downhole tool formed from the solidified extrusion-decomposable resin molded product or secondary molded product or a member thereof according to the present invention includes a solidified extrusion-decomposable resin molded product or secondary molded product itself, as well as a solidified extrusion. It includes a combination of a decomposable resin molded product or a secondary molded product and other members (members made of metal, inorganic material, resin, rubber, etc. can be used).

[Ball sealer, ball seat, flack plug and bridge plug]
The downhole tool or its member derived from the decomposable resin composition for solidification extrusion molding of the present invention is in contact with various members used for well drilling under the condition that the mining conditions such as deepening are severe and diverse. It is particularly preferable to use a downhole tool selected from the group consisting of a ball sealer, a ball seat, a flack plug, and a bridge plug, or a member thereof.

V. Hydrocarbon Resource Recovery Method The hydrocarbon resource recovery method of the present invention is a solidified extrusion decomposable resin molded product formed by solid extrusion molding the above-described solidification extrusion decomposable resin composition of the present invention, or As long as the method is a hydrocarbon resource recovery method using a downhole tool formed from a solidified extrudable resin secondary molded product formed by machining the solidified extrudable resin molded product or a member thereof, It is not limited. By using the downhole tool or the member thereof according to the present invention, the mining conditions such as deepening become severe and diverse, and it has sufficient tensile properties and is derived from toughness. It has excellent toughness that it is difficult to damage even if it contacts or collides with the components used for well drilling, and it can be easily removed as necessary, contributing to cost reduction and process shortening of well drilling A method for recovering hydrocarbon resources is provided.

For example, the hydrocarbon resource recovery method of the present invention performs drilling and fracturing of a downhole using the downhole tool of the present invention or a member thereof selected from a ball sealer, a ball seat, a flack plug, and a bridge plug. Is the method. By using the downhole tool or the member thereof according to the present invention, the downhole tool or the member has sufficient mechanical strength and comes into contact with or collides with members used for well drilling due to toughness. However, since it has high impact resistance that is difficult to damage, a method for recovering hydrocarbon resources that can reduce costs and shorten processes required for drilling a well is provided. Furthermore, by using the downhole tool of the present invention or a member thereof, the degradable resin can be decomposed by biodegradation, hydrolysis or other methods under various well environmental conditions as required. Also, since the removal of the downhole tool or its members can be easily performed, there is provided a hydrocarbon resource recovery method that is effective in reducing the cost required for drilling a well and shortening the process.

EXAMPLES The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to the examples. In the examples and comparative examples, the materials contained in the decomposable resin composition for solidification extrusion molding, and the measurement methods for the physical properties and characteristics of the solidification extrusion decomposable resin composition and the solidification extrusion decomposable resin molded article are as follows. It is as follows.

[Melt viscosity]
The melt viscosity of the degradable resin contained in the decomposable resin composition for solidification extrusion molding was measured at a temperature of 270 ° C. and a shear rate of 122 sec ⁻¹ using a capillograph [Capiro 1A manufactured by Toyo Seiki Seisakusho Co., Ltd.] Unit: Pa · s).

[Izod impact strength (no notch) and Izod impact strength (notched)]
The Izod impact strength (without notch) of the solidified extrusion molding decomposable resin composition and the solidified extrusion decomposable resin molded product was determined using a pendulum type impact tester (stock) using the test piece prepared by the method described above. Using a Toyo Seiki Seisakusho Co., Ltd. hammer mass 120 kg), the Izod impact strength (no notch) was calculated by measuring an unnotched test piece at room temperature in accordance with ASTM D256 (corresponding to ISO 180) ( The average value of n = 5 (unit: J / m). In addition, Izod impact strength (notched) is measured on a notched specimen at normal temperature in accordance with ASTM D256 using a pendulum impact strength (manufactured by Ueshima Seisakusho, hammer mass 40 kg). It was calculated by performing.

[Tensile strength]
The tensile strength of the decomposable resin composition for solidification extrusion molding and the solidification extrusion decomposable resin molded product was determined using 2t Autograph AG-2000E manufactured by Shimadzu Corporation using the test piece prepared by the method described above. In accordance with JIS K7113, it was measured and calculated at a speed of 50 mm / min at room temperature (average value of n = 5, unit: MPa).

[Tensile elongation]
The tensile elongation of the decomposable resin composition for solidification extrusion molding was measured using a 2t autograph AG-2000E manufactured by Shimadzu Corporation in accordance with JIS K7113 at a speed of 50 mm / min. (Average value of n = 5. Unit:%).

[Example 1]
The following materials:
Decomposable resin: 70% by mass of PGA (manufactured by Kureha Co., Ltd., melt viscosity 900 Pa · s), and reinforcing material: glass fiber [trade name chopped strand 03JAFT592S, manufactured by Owens Corning Japan] 30% by mass (degradable resin and reinforcing material Is mixed at a temperature of 230 to 250 ° C. for 5 minutes using a 23 mmφ twin screw extruder (2D25S manufactured by Toyo Seiki Seisakusyo Co., Ltd.) with L / D = 25, and then injected. Using a molding machine, samples for measuring physical properties and characteristics were prepared, and a decomposable resin composition for solidification extrusion molding was obtained. About the obtained decomposable resin composition, Izod impact strength (without notch), Izod impact strength (with notch), tensile strength and tensile elongation (hereinafter collectively referred to as “toughness and tensile properties”) ) Was measured and calculated. The results are shown in Table 1 together with the composition of the decomposable resin composition for solidified extrusion molding. In addition, by solidifying and extruding the decomposable resin composition for solidified extrusion, a round bar-shaped solid extruded and decomposable resin molded product having a diameter of 80 mm could be obtained. No cracks or the like were found in the round bar-shaped solidified extrusion-decomposable resin molded product. The test piece cut in the TD direction from the vicinity of the outer peripheral surface of the solidified extrudable resin molded product has an Izod impact strength (without notch) of 321 J / m, an Izod impact strength (with notch) of 66 J / m, and a tensile strength. The test piece similarly cut in the MD direction had an Izod impact strength (without notch) of 226 J / m, an Izod impact strength (with notch) of 54 J / m, and a tensile strength of 100 MPa. In addition, the Izod impact strength (without notch) of the test piece cut out in the MD direction from the central vicinity of the solidified extrusion-decomposable resin molded product is 233 J / m, the Izod impact strength (with notch) is 46 J / m, and tensile. The strength was 106 MPa.

[Example 2]
Example 1 except that the composition of the decomposable resin composition for solidification extrusion molding was changed to 90% by mass of PGA and 10% by mass of the reinforcing material (the total of the decomposable resin and the reinforcing material was 100% by mass). In the same manner as above, a decomposable resin composition for solidification extrusion molding was obtained. The toughness and tensile properties of the obtained degradable resin composition were measured and calculated. The results are shown in Table 1 together with the composition of the decomposable resin composition for solidified extrusion molding. In the same manner as in Example 1, a round bar-shaped solid extrusion-decomposable resin molded product having a diameter of 80 mm could be obtained from the solidification extrusion-decomposable resin composition. No cracks or the like were found in the round bar-shaped solidified extrusion-decomposable resin molded product.

[Example 3]
The composition of the decomposable resin composition for solidification extrusion molding is 69.6% by mass of PGA, 30% by mass of reinforcing material, and
Toughness improver: Polyester / polyether block copolymer [polybutylene terephthalate / polyether block copolymer manufactured by DuPont, trade name Hytrel (registered trademark) 3078] 0.4% by mass (degradable resin, reinforcing material and toughness improvement) The total amount of the agent was 100% by mass.) A decomposable resin composition for solidification extrusion molding was obtained in the same manner as in Example 1 except that the agent was changed to 100% by mass. The toughness and tensile properties of the obtained degradable resin composition were measured and calculated. The results are shown in Table 1 together with the composition of the decomposable resin composition for solidified extrusion molding. In the same manner as in Example 1, a round bar-shaped solid extrusion-decomposable resin molded product having a diameter of 100 mm could be obtained from the solidification-extrusion decomposable resin composition. The round bar-shaped solidified extrusion-decomposable resin molded product had a uniform cross-sectional shape, and no cracks were observed. In addition, although it was a large-diameter round bar having a diameter of 100 mm, the occurrence of central whitening due to stress concentration was not observed.

[Example 4]
The composition of the decomposable resin composition for solidification extrusion molding was set to 69.3% by mass of PGA, 30% by mass of reinforcing material, and 0.7% by mass of toughness improver (the total of decomposable resin, reinforcing material and toughness improving agent was 100% by mass) Except that it was changed to), a decomposable resin composition for solidification extrusion molding was obtained in the same manner as in Example 3. The toughness and tensile properties of the obtained degradable resin composition were measured and calculated. The results are shown in Table 1 together with the composition of the decomposable resin composition for solidified extrusion molding. In the same manner as in Example 3, a round bar-shaped solid extrusion-decomposable resin molded product having a diameter of 100 mm could be obtained from the solidification extrusion-decomposable resin composition. The round bar-shaped solidified extrusion-decomposable resin molded product had a uniform cross-sectional shape, and no cracks or central whitening were observed.

[Example 5]
The composition of the decomposable resin composition for solidification extrusion molding is 67.9% by mass of PGA, 30% by mass of reinforcing material, and 2.1% by mass of toughness improver (the total of decomposable resin, reinforcing material and toughness improving agent is 100% by mass). Except that it was changed to), a decomposable resin composition for solidification extrusion molding was obtained in the same manner as in Example 3. The toughness and tensile properties of the obtained degradable resin composition were measured and calculated. The results are shown in Table 1 together with the composition of the decomposable resin composition for solidified extrusion molding. In the same manner as in Example 3, a round bar-shaped solid extrusion-decomposable resin molded product having a diameter of 100 mm could be obtained from the solidification extrusion-decomposable resin composition. The round bar-shaped solidified extrusion-decomposable resin molded product had a uniform cross-sectional shape, and no cracks or central whitening were observed.

[Example 6]
The composition of the decomposable resin composition for solidification extrusion molding is 67.2% by mass of PGA, 30% by mass of reinforcing material, and 2.8% by mass of toughness improver (the total of decomposable resin, reinforcing material and toughness improving agent is 100% by mass). Except that it was changed to), a decomposable resin composition for solidification extrusion molding was obtained in the same manner as in Example 3. The toughness and tensile properties of the obtained degradable resin composition were measured and calculated. The results are shown in Table 1 together with the composition of the decomposable resin composition for solidified extrusion molding. In the same manner as in Example 3, a round bar-shaped solid extrusion-decomposable resin molded product having a diameter of 100 mm could be obtained from the solidification extrusion-decomposable resin composition. The round bar-shaped solidified extrusion-decomposable resin molded product had a uniform cross-sectional shape, and no cracks or central whitening were observed.

[Comparative Example 1]
A decomposable resin composition was obtained in the same manner as in Example 1 except that the composition of the decomposable resin composition was changed to one consisting of 100% by mass of PGA (does not contain a reinforcing material and a toughness improver). It was. The toughness and tensile properties of the obtained degradable resin composition were measured and calculated. The results are shown in Table 1 together with the composition of the degradable resin composition.

[Comparative Example 2]
The composition of the degradable resin composition is 86.4% by mass of PGA, 10% by mass of the reinforcing material, and 3.6% by mass of the toughness improver (the total of the decomposable resin, the reinforcing material, and the toughness improving agent is 100% by mass). In the same manner as in Example 1, a decomposable resin composition was obtained. The toughness and tensile properties of the obtained degradable resin composition were measured and calculated. The results are shown in Table 1 together with the composition of the degradable resin composition.

[Comparative Example 3]
The composition of the degradable resin composition was changed to PGA 66% by mass, reinforcing material 30% by mass, and toughness improver 4% by mass (the total of degradable resin, reinforcing material and toughness improving agent is 100% by mass). Except for this, a decomposable resin composition was obtained in the same manner as in Example 1. The toughness and tensile properties of the obtained degradable resin composition were measured and calculated. The results are shown in Table 1 together with the composition of the degradable resin composition.

From Table 1, the decomposable resin compositions for solidification extrusion molding of Examples 1 to 6 have a decomposable resin content of 60 to 97% by mass when the total of the decomposable resin, the reinforcing material and the toughness improver is 100% by mass. A decomposable resin composition for solidification extrusion molding containing 3 to 37% by mass of a reinforcing material and 0 to 3.5% by mass of a toughness improver, and having an Izod impact strength (no notch) of 500 J / m or more, It was confirmed that the Izod impact strength (with notch) was 50 J / m or more and the tensile strength was 135 MPa or more. In addition, the decomposable resin compositions for solidified extrusion molding of Examples 1 to 6 have an Izod impact strength (with notch) of 1 / 8.6 to an Izod impact strength (without notch). 1 / 7.4.

In addition, the round bar-shaped solid extrusion extrudable resin molded product formed by solidification extrusion molding of the solidification extrusion molding decomposable resin compositions of Examples 1 to 6 has an Izod impact strength (no notch) of 150 J /. It was found to have balanced mechanical properties such as m or more, Izod impact strength (notched) of 30 J / m or more, and tensile strength of 60 MPa or more. Therefore, from the solidified extrusion decomposable resin molded product or the secondary molded product formed by solidification extrusion molding of the solidification extrusion molding decomposable resin composition of Examples 1 to 6, for example, downhole for well drilling If the tool or its member is formed, the mining conditions such as deepening will be severe and diverse, and it will have sufficient mechanical strength and resistance to contact and collision with various members used for well drilling. It has an impact property, and further has a decomposability that can be easily removed from the well as needed, so that it is estimated that it can contribute to cost reduction and process shortening of the well drilling. It was.

In particular, the decomposable resin compositions for solidification extrusion molding of Examples 3 to 6 contain Izod impact strength (no notch) and Izod impact strength by containing a toughness improver of 3.5% by mass or less together with a reinforcing material. It was confirmed that the thickness (with notch) can be improved in a well-balanced manner, and a solidified extrudable resin molded product having a large diameter of 100 mm can be obtained without causing central whitening or cracking due to stress concentration. It was also found that solidified extrusion decomposable resin molded articles can be formed by solidifying and extrusion molding the decomposable resin compositions for solidified extrusion molding of Examples 3 to 6.

On the other hand, the decomposable resin composition of Comparative Example 1 containing no reinforcing material has small values of Izod impact strength (without notch), Izod impact strength (with notch) and tensile strength. It was confirmed. In the decomposable resin composition of Comparative Example 1, the magnitude of the Izod impact strength (with notch) relative to the magnitude of the Izod impact strength (without notch) was 1 / 14.4. According to the decomposable resin composition of Comparative Example 1, for example, if a downhole tool for well excavation or a member thereof is formed from a solidified extrusion decomposable resin molded product or a secondary molded product, mining such as deepening is performed. Under severe and diverse conditions, it cannot be said that it has sufficient mechanical strength, and lacks impact resistance against contact and collision with various members used for well drilling. Was inferred.

Moreover, although containing degradable resin, a reinforcing material, and a toughness improving agent, content of a toughness improving agent is 3.5 mass% (the sum total of a degradable resin, a reinforcing material, and a toughness improving agent is 100 mass%.) It was confirmed that the decomposable resin compositions of Comparative Examples 2 and 3 exceeding the above values were both small in Izod impact strength (no notch) and tensile strength. According to the decomposable resin compositions of Comparative Examples 2 and 3, for example, if a downhole tool for well excavation or a member thereof is formed from a solidified extrusion decomposable resin molded product or a secondary molded product, the depth is increased. It cannot be said that it has sufficient mechanical strength under the severe and diverse mining conditions, etc., and it lacks impact resistance against contact and collision with various members used for well drilling. It was inferred that there was.

[Example 7]
Decomposable resin composition for solidification extrusion molding in the same manner as in Example 6 except that the reinforcing material was changed to milled fiber (milled fiber EFH50-31 manufactured by Asahi Glass Co., Ltd., fiber diameter 11 μm, fiber length 50 μm). Got. That is, the composition of the decomposable resin composition for solidification extrusion molding was 67.2% by mass of PGA, 30% by mass of reinforcing material, and 2.8% by mass of toughness improver (the total of degradable resin, reinforcing material and toughness improving agent is 100% by mass). From this decomposable resin composition for solidification extrusion molding, a round bar-shaped solid extrusion extrusion decomposable resin molded product having a diameter of 100 mm could be obtained in the same manner as in Example 6. No cracks or central whitening were observed in the round bar-shaped solidified extrusion-decomposable resin molded product.

In the present invention, when the total of the decomposable resin, the reinforcing material and the toughness improving agent is 100% by mass, the decomposable resin 60 to 97% by mass, the reinforcing material 3 to 37% by mass, and the toughness improving agent 0 to 3. A decomposable resin composition for solidification extrusion molding containing 5% by mass, having an Izod impact strength (without notch) of 500 J / m or more, an Izod impact strength (with notch) of 50 J / m or more, and a tensile strength Is a decomposable resin composition for solidification extrusion molding characterized by being 135 MPa or more, suitable for forming a solidified extrusion resin molded product or forming a solidified extrusion resin secondary molded product by machining, For example, it is a solidified extrusion molding resin composition suitable for applications such as downhole tools for well drilling or its members, and has balanced mechanical properties such as impact resistance and mechanical strength and moldability. , The resin composition for solidified extrusion molding having decomposability can be provided, and further, the solidified extruded resin molded product or the secondary molded product, and the downhole tool formed from the solidified extruded resin molded product or the secondary molded product In addition, since it is possible to provide a member and a method for recovering hydrocarbon resources using the downhole tool or the member, the industrial applicability is high.

Claims (12)

When the total of the decomposable resin, the reinforcing material and the toughness improving agent is 100% by mass, the decomposable resin 60 to 97% by mass, the reinforcing material 3 to 37% by mass, and the toughness improving agent 0 to 3.5% by mass are added. A decomposable resin composition for solidification extrusion molding containing:
The above-described decomposable resin for solidification extrusion molding characterized by having an Izod impact strength (without notch) of 500 J / m or more, an Izod impact strength (with notch) of 50 J / m or more, and a tensile strength of 135 MPa or more. Composition. The decomposable resin composition for solidification extrusion molding according to claim 1, wherein the decomposable resin is an aliphatic polyester. The degradable resin composition for solidified extrusion molding according to claim 1 or 2, wherein the degradable resin is polyglycolic acid. The decomposable resin composition for solidification extrusion molding according to any one of claims 1 to 3, wherein the toughness improver contains a thermoplastic elastomer. The decomposable resin composition for solidified extrusion molding according to claim 4, wherein the thermoplastic elastomer is a thermoplastic polyester elastomer. 6. The decomposable resin composition for solidification extrusion molding according to claim 5, wherein the thermoplastic polyester elastomer is a polyester / polyether block copolymer or an aromatic polyester / aliphatic polyester block copolymer. When the total of the degradable resin, the reinforcing material, the toughness improving agent and the chain extender is 100% by mass, the decomposable resin is 60 to 97% by mass, the reinforcing material is 3 to 37% by mass, and the toughness improving agent is 0 to 3.5. The decomposable resin composition for solidified extrusion molding according to any one of claims 1 to 6, comprising 0% by mass and 0 to 3% by mass of a chain extender. A solidified extrudable resin molded product formed by solidifying and extrusion-molding the decomposable resin composition for solidified extrusion molding according to any one of claims 1 to 7. A solidified extrudable resin secondary molded product formed by machining the solidified extrudable resin molded product according to claim 8. A downhole tool or a downhole tool member formed from the solidified extrudable resin molded product according to claim 8 or the solidified extrudable resin secondary molded product according to claim 9. The downhole tool or the downhole tool member according to claim 10 selected from the group consisting of a ball sealer, a ball seat, a flack plug, and a bridge plug. A hydrocarbon resource recovery method using the downhole tool or the downhole tool member according to claim 10 or 11.