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`W02014109347
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`Poly-l-lactlc aCld solidified and ext-rusmn-
`molded article, method for producmg same,
`-
`-
`in? use applications Of same
`sets 2034109347 A1
`
`ABSTRACT
`A poly-L-lact:c aCld (PLLA) solidified and extrusion~molded article which
`_
`comprises a resin material containing a PLLA haying a weight average
`molecular weight of 100,000 to 380,000, a melt ViscoSlty (temperature. 2407;,
`shear rate: 120 sec?) of 20 to 2,000 Pa‘s and an L—form content of 80 to 100%.
`
`and has a thickness or diameter of 10 to 500 mm and tensile strength of 5 to
`100 MPa at 66"C (wherein the article may additionaily contain a filler; in this
`
`Publication number
`Publication type
`Application number
`Publication date
`Filing date
`Priority date
`
`Also published as
`
`Inventors
`
`Applicant
`Export Citation
`
`“02014109347 A1
`Application
`PCTIJP2014/050184
`Jul 1.7. 2014
`Jan 9, 2014
`Jan 11. 2013
`
`oAzsarasom. cameras-ac
`CN'30493FGSOA. i)82015033541311
`
`tw‘lasayuki Okui'a, 3:1:‘5’ AESVE:
`
`‘lakeo Taltahashi Hiroyuiizl Sate. it;
`.
`Kureha Corporation, ~, =':'_
`
`BiBTex EndNote. RetMan
`
`
`_ Referenced by 54:: Classifications tel},
`Patent Citations i‘
`
`---’
`2-393; EVEN-3 ‘-
`L
`
`case the tensile strength of the article may be 5 to 200 MPa): a downhole tool
`member or ball sealer for well drilling use. which is formed by machining the
`solidified and extrusion—molded article; a sealing plug equipped With the
`downhole tool member; a method for producing a PLM solidified and extrusion~molded article, which comprises the steps of supplying a resin material containing a
`PLLA into an extruder. carrying out the solidification and extiu5lon molding of the resin material, pressurizing the resultant solidified and extruded product. and then
`drawing the pressurized product while applying a back pressure in the direction of a forming die to thereby prevent the expansion of the solidified and extruded
`product; and a wet: drilling method
`
`External Links: Patentscope Espacenet
`
`
`HIAGES
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`Poly ~t.~ lactic acid solidified extrudate and its manufacturing method and its
`application
`
`1. The weight average molecular weight of 100.000 to 380,000, a
`
`temperature of 240 "C and an :\ rate melt viscosity measured at 1205ec
`
`The present invention relates to poiylactic acid ~L- solidified extrudate and a
`method for producing the same and their applications. More particularly, cutting
`dl'iiiingi deSlred secondary molded product thickness which can be molded into
`or diameter of the polylactic acid -L- solidified extrudate shapes and a method
`of manufacturing by machining such as cutting, as well as, on the downhole tool
`member and well drilling method ball sealer or for well drilling for the weil drilling
`
`‘1 is 20 ~ 2,000Pa - s, and, L form proportion of 80-100% made of a resin
`material containing a polylactic acid -L- has a thickness or diameter of 10
`~ 500mm, a tensile strength of 5 ~ 100MPa at a temperature 66 "C’
`polylactic acid -l_— solidified extrudate.
`
`is formed from the poly «L— lactic acid solidified extrudate. Resin mottled product having a three-dimensional shape or complex shape. is
`
`generally molded by injection molding According to the injection moiding. it is
`possible to mass-produce a molded product having a destred shape However,
`in order to produce by ihiection molding a molded product that require high
`dimensmnal accuracy. it is necessary an expensive mold having a high
`
`P
`i
`dimenswnai accuracy Moreover. lflleCthii molding, since it is easny deformed
`by the shrinkage and resrdual stresses after the injection molding. and
`depending on the properties of the molded product of the shape and the reset
`material. it is necessary to preciseiy adjust the die shape. in injection molding.
`because of the high failure rate, often the product is costly. Further in the
`
`3_ The weight average molecular weight of 1001000 to 350‘000. a
`temperature of 240 of and shear rate melt viscosity measured at 1205ec
`‘1 is 20 ~ 2,000Pa s, and, L form proportion of 80-10095 with poly —L-
`add, :5 resin materiai containing 5 to 70 wt% of the filler in total amount
`(the total amount of the resin material is 100 wt%). and has a thickness
`or diameter of 10 ~ 500mm > poly lactic acid 4: solidified extrudate
`
`
`3:
`4. n
`f;
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`Patent W02014109347A1 — Poly-l-lactic acid solidified and extrusion-molded article, met... Page 2 of 20
`
` :nn molding there is a shrinkage and residual stress. it is difficult to mold a
`large ...olded product thickness
`
`in order to obtain a molded article having a three-dimensional shape or a
`complicated shape, the resrn materiai is extruded, flat, round bar, pipe, a
`material for machining having various shapes such as atypical products
`5material?or cutting“ is referred to it have) were prepared, cut into the machine
`for processtng materiai, drilling a method of molding a secondary molded article
`having a desired shape is subjected to mechanical processing such as cutting,
`are known, The method of machining a materiai for machining, since it requires
`no expensrve molds can be produced to yield low molding at relatively low cost,
`it can cope with frequent changes in the specifications of the molding.
`dimensionai accuracy that a high molding was obtained, and has advantages
`such that it is possible to manufacture a molded product having a complicated
`shape and a large thickness which is not suitable for iniection molding
`
`However, in any plastic material or extrudate, it is not suitable for the material
`for machining, The material for machining. for example, it is excellent in
`mechanical workability in thickness the residual stress is small
`it does not
`
`cause deformation and distort-3: Lian overly heating to the frictional heat
`
`ng with high precision such that it can
`generated during machining, the mac
`have been required to satisw a high degree of required properties
`
`The machining of polymeric material, in general, most of the processmg
`methods used in the metallic material is used as is. Be formed by extruding,
`conventional film or sheet, iarge flexibility in thin such tubes are not suitable for
`mechanical processing such as cutting, Even extrudate having a shape, such
`as thickness or diameter is large flat or round bar. extrudate residual stress
`during extrusion is too large. easiiy deformed after the time of machining or
`machining, dimensional accuracy it is difficult to obtain a high secondary
`molding Restriual stress may be an extruded product with reduced. cutting,
`driil--ng which tends to generate cracks or cracks at the time of mechanicall
`processing such as cutting, not suitable material for machining.
`
`To obtain material for machining with characteristics suitable for machining by
`‘t of the resin material, a
` extrusion molding, i
`
` necessary to devote the se'
`
`contrivance such as the extrusion molding method Therefore, conventionaiiy.
`by usrng a resin material containing a generai~purpose resin. engineering
`plastics. for extrusion molding method for the production of extrudates suitable
`for material for machining. various proposals have been made,
`
`For example. Patent Document 1, polyetheretherketone, poiyetherimide,
`polyphenyiene sulfide, pclysuifone, polyether sulfone, and solidified extrusion—
`rnolding a resm composttion containing engineering plastic such as
`polycarbonate 3mm excess thickness or diameter Method for producing a
`material for machining withis \.is
`
`On. the other hand, as a friendly polymer materials environmentally degradable
`plastics have been focused, extrudates such as films and sheets. blow molded
`articles, such as bottles. application deployment have been made to such as
`injection molding. in recent years, it is also required increased for application to
`a biodegradable plastic of machining for the material.
`
`Poiylactic actd is known as a representative biodegradable plastic, because it
`has a moderate rate of degradation, depending on the application and the
`environment it is a biodegradable plastic which are preferably used. Furtherr
`
`poiylactic acid, greenhouse effect gas circulating Sir
`:t is a polymeric material
`obtained by polymerizing the lactic acid obtained by fermenting a sugar taken
`from the plantwderived raw materials such as maize, even when the combustion
`process in the enVironment it has a carbon offset property that does not
`increase the emissions of CO 2 :5
`
`By the way, from the growing interest in the resource constraints. oil (shale oil,
`etc.) -:‘in the present invention. may be sxrnply referred to as "Oil“.l Hydrocarbon
`
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`Patent WO2014109347A1 - Poly—l-laotic acid solidified and extrusion—molded article, met... Page 3 of 20
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`including the For downhole provided li’l order to perform well driiling for
`recovering hydrogen resources (holes provided for forming an underground
`welibore.
`weli or well. such as gas weiis). even higher depth of the
`enlargement progresses They are out. For example, in a horizontal welt bore.
`which is formed by embedding a substantially horizontally in the shale layer or
`the iike over the underground 1,000m. a method of performing hydraulic
`fracturing (the fracturing} has become widespread. Ball sealers and for sealing
`perforations of (fractures) formed by hydraulic fracturing. downhole tools for well
`di‘dili‘lQ that is installed downhole in order to carry out the hydraulic fracturing
`(hereinafter simply be referred to as "downhoie tool" a} a is Flack plug. bridge
`plug. packer. such as the sealing plug, such as a cement retainer is to stop eye
`the place that made the hydraulic fracturing before and place of the vicmity of
`the distal end of the down hole. new. or again by carrying out the hydrauilc
`fracturing, after forming a perforation (fractures). and is recovered or destroyed,
`
`Therefore,
`1 ball sealers. welt drilling for the downhole tool member provrded
`in the downhole tool such as the sealing plug (hereinafter sometimes referred to
`simply as "downhole tool member“). l bear in hydraulic fracturing and laying
`strength (eg. tensrle strength} and which has a cost. ease of recovery or
`destruction is sought.
`
`Flack plugs. bridge plugs. packers. cement retainer. etc. of the seating piug
`(hereinafter. simply referred to as "piug“.} ls rubber usually around a mandrel
`plug (sometimes referred to as "mandrel" ) It is of the structure in which
`mounting Say of sealing member. the sealing mechanism of the sealing plug.
`the tensile and f or compression of the core rod (mandrel). rubber express
`sealang action by deforming (Patent Documents 2 and 3). The SIZe of the plug
`core rod (mandrel) as the maximum inner diameter of the downhole. as long as
`it Is possible to attach a rubber-made sealing member around and formed into
`any predetermined outer diameter. often 70 it is ~ ‘lOOmm. Moreover. mandrel
`plug (mandrei). many in order to pass the mud has a hollow shape. the hollow
`
`has
`often 10 ~ 50mm. typically 19 1mm (0 75 inches} 25 4mm (‘- inch).
`and a 31.8mm (1.25 inch}. for example. the main portion of the piperiike shape
`of the length ofabout 1.000mm. at both ends and pulling the seed rod (mandrel)
`and r' or Jig for performing compression is a shape with the enlarged diameter
`portion so as to be able to engage the. in the tensile and i or compression of the
`plug core rod (mandrel). about 1500 ~ 5,000kgf (about 14.700 ~ 49.000N}. in
`many cases. about 2.000 ~ 4.500kgf (about 19 _, subjected high load of 600 ~
`44.100N) is the core bar (mandrel). in particular, the core rod (engaging portion
`Wlth the aforementioned diameter expansion portion (jig of the mandrel». 2—5
`times of stress Because the concentration is. it is necessary to select a material
`that has the strength to withstand these high loads.
`
`27.
`
`Foltowing steps 1 through 4;
`1) weight average molecular weight of 150,000 to 540,000, temperature
`
`240 °C and a shear rate of tZOSec ‘1 in the measured melt viscosity of 30
`~ 3.000Pa - s, and poly-L-body ratio is 80-100% The resin material
`containing -L- lactic acid, is fed to an extruder and melt-kneaded at a
`cylinder temperature of 195 ~ 260 °C extruder step 1.
`2) from the extrusrorl die of the extruder tip. a restn material which is
`melted by melt-kneading. a channel having a cross-sectional shape of
`the molten resin passage and communicating and extruded product of
`the extrusion die. the forming die and a cooling means step of extrusion
`into the flow channel 2;
`3) it is solidified by cooling the forming die flow path melt extrudate
`comprising a restn material. then step 3 is extruded solidified extrudate to
`the outside from the tip of the forming die; a and 4) solidifying the
`extrudate is pressurized Te. and receipt while applying back pressure in
`the forming die direction, that time. by suppressing the expansion in the
`thickness direction or radial direction of the solidified extrudate by
`pressure. the thickness or diameter obtain a solidified extrudate of 10 -~
`500mm Step 4;
`10 to have a thickness or diameter of 500mm. the production method of
`
`poly
`0 acid -L- solidified extrudate tensile strength at a temperature 66
`°C is 5 ~ 100MPa including the.
`
`28.
`
`Following steps 1 ’to 4;
`l
`') weight average molecular weight of 150.000 to 540.000, temperature
`
`After the implementation of the hydraulic fracturing IS, it can recover the sealing
`member. a method of or destroy the core rod (mandrel) for forming an opening
`is adopted. As the mandrel oi the plug (mandrel). conventionalty. since the
`metal of the cast iron or the like is used. it takes a high cost in recovery of the
`sealing plug. the difficulty in breaking of the metal core bar (mandrel: was a
`difference To the high cost. The plug core rod (mandrel). have come to be
`carried out the use of epoxy resin compostte material or the like. However. restn
`composite material such as an epoxy resin composite material. the strength is
`not sufficrent. it takes a high cost for the recovery of the sealing member :s the
`same resm and reinforcing material after breaking the core rod (mandrel)
`(carbon fiber. metai fiber. etc.) because it is non-degradable treatment or
`disposal i have a problem is virtually :mpossible.
`
`240 °C and a shear rate of tZOSec “ in the measured melt viscosity is 30
`~ 3.000Pa s and. is a Luisomer ratio is 80-“loo% with poly -L- acid. a
`resin material containing 5 to 70 wt% of the filler in total amount (the total
`amount of the resin material is 100 wt%.). was fed to an extruder.
`extruder cylinder temperature 195 is melt-kneaded at ~ 260 °C step t ‘;
`2) from the extrusion die of the extruder tip. a resin material which is
`melted by melt-Kneading. a channel having a cross-sectional shape of
`the molten resin passage and communicating and extruded product of
`the extrusion die, the forming die and a cooling means step of extrusion
`into the flow channel 2;
`3) it is solidified by cooling the forming die flow path melt extrudate
`comprising a resin material. then step 3 is extruded solidified extrudate to
`the outside from the tip of the forming die; a and 4) solidifying the
`extrudate is pressurized Te. and receipt while applying back pressure in
`the forming die direction. that time. by suppressing the expansion in the
`‘i’ry the new (Boogie Patents. wltn mashinwolassified (Beagle echoiar results, and Japa‘lflfiflééWflttoiPfifidfiFfiflé‘bfion of the solidified extrudate by
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`Also, the ball sealers are aiso conventionally made of non-degradable material
`of the rubber~~coated nylon, or the like nonmdegradable plastics and aluminum.
`
`such as a phenolic. resm. for sealintd '
`*. if necessary. to compare that
`the diameter 16 - 32mm those target small has been used However. in recent
`years. with an increase in depth of the size of the downhole have larger
`diameter. for example a diameter of 25 ~ 100mm. or even a large diameter. a
`request for a bail sealer having a strength to withstand a high load is spread
`
`httpsz/i’www.googlc.cornipatcnts/WOZO14109347A1?cl===en&dq:WO2014109347&hl=en...
`
`10;"111’2017
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`
`Downhoie too: member or ball sealers {hereinafter sometimes referred to as
`
`“downhole tool member. and the like" )AS, without recovering the ground -
`
`use. it can be disintegrated by keep leaving in the downhole S
`it is, the use
`of degradable plastics is expected. Specifically. it has a suffiCient strength
`(temperature environments in excess of 65 ”Cl environment that exceeds the
`underground 1.000rn, diverse together are capable of forming a downhole too:
` ‘= in step a so
`unified extrudate obtain
`as “M ..
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`members such as the desired shape and depth degradable plastic and a
`molded product such as a possible decomposition is adapted to be determined
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`Patent W02014109347A1 - Poly-l-lactic acid solidified and extrusion—molded article, met... Page 4 of 20
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`pressure. the thickness or diameter obtain a solidified extrudate of 10 ~
`500mm Step 4;
`10 to have a thickness or diameter of 500mm, the production method of
`polylactic acid ~L— solidified extrudate tensile strength at a temperature 66
`"C is 5 ~ 200MPa including the.
`
`However. many of them with a degradable plastic is a crystalline resin iniection
`molding or compression molding, by a general purpose method of a resm
`molding, such as melt extrusion molding, and to produce a molded product,
`such as a downhole tool member. after shaping it { shrinkage and voids due to
`shrinkage accompanying the thermal contraction and crystallization after
`
`39'
`
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`
`molding) occurs, the dimensional accuracy required is not obtained. Therefore,
`in order to obtain the downhole tool member such as a method in which the
`
`.51,
`
`thickness or diameter formed by the solidification extrusron molding from a
`degradable plastic machining such as cutting large solidified extrudate has
`attracted attention.
`
`
`
`Polylactic acid, a representative biodegradable plastic. it is known to use in a
`wellbore. such as on drilling Patent Document 4, weilbore treatment fluid
`vrscosrty containing polyiactic acid, together with the sand control screen or coating. mechanical devaces or components
` rhc dos-:1 :s disclosed as a mechanical device. the packer . bridge plug or
`thereof are arranged in iuchi pit formed poly-i
`cement retainer etc. are exemplified.
`
`\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\
`
`Patent Document 4. furthermore, from a crystalline poly -D- lactide (polylactic add). the bending strength of the rod-
`
`shaped body to be manufactured by :n when molding. it is in the range of 40 ~ l40MPa. and is solidified by extrusion rod-
`shaped body to be formed is described as having a flexural strength of up to ZOOMPaK refer to "Biomateriais 17 (March
`
`1996, 529—535)“ (Non—Patent Document l). Non-Patent Document 1.. as a "soli
`‘
`:19 improvement in mechanical
`properties of the polylactic acid by extrusmn". My {viscosity average molecular weight) of 160,000 rod from a poly-lactide
`»D- become solidified Circular cross section manufactured by extrusion of There are listed, the mechanical properties of
`yield bending strength, etc. of the solidified extrudates are disclosed specifically a round bar having a diameter of 4mm
`
`A round rod in a solidified extrudate diameter 4mm disclosed in Non—Patent Document 1. specrficaliy. the shape and see of
`the downhole required along with a high depth of the size of the recent dcwnhoie it is not possible to form a tool member.
`and the like. Then. the solidified extrudate rod-shaped body or the like formed from poly —D- lactide as disclosed in Patent
`Document 4 or Non~Patent Document 1. since the glass transition temperature of the polylactic aCld is a 55 ~ 60 "t“. it has
`sufficient strength (temperature environments in excess of 65 “Cl environment that exceeds the aforementioned
`underground 1,000m, whether those capable of forming a downhole tool members such as the desrred shape was
`unknown.
`
`Patent Publication No. 2005—226031 {US PatentAppllcation Publication No. 20081038517 Patent specification
`correspondence) US Patent Application Publication No. 2005/205265 US Patent Application Publication No. 33:}: 1/277989
`US Patent Application Publication No 20041231845
`
`" Enhancement of the mocha-meal Properties of Polylactzdes by sc=id state extrusion Biomaterials 1996. Vol 17, No.5
`(1996952). pp 529 ~ 535
`
`The object of the present invention has a setting, drilling. secondary molded article having a desired shape by mechanical
`
`. merits in excess of 65 “(i‘) environment
`processing such as cutting. in particular a sufficient strength (temperature envi
`that exceeds the underground 1.000m. The present invention is to provide a desired solidified extrudate of biodegradable
`plastics which can be formed downhole tool members such as the shape and manufacturing method. and its applications
`
`The present inventors have found. as a result of :ntensive studies to solve the above problems, by the ratio of L- lactic acid
`is to select a high poiylactic acid. in an enVironment (greater than 65 "t‘ temperature environment, etc.) that exceeds the
`underground '3 ,C-OOm . and it found that the solidified extrudate having excellent strength that can not be anticipated from
`the solidified extrudate formed from polylactic —D- acid disclosed in Patent Document 4 is obtained, and have completed
`the present invention.
`
`That is. according to the present invention, the weight average molecular weight of 100.000 to 380,000, the melt Viscosity
`
`measured at a temperature 240 *1: and a shear rate of izosec "' is 20 ~ 2‘000Pa ~ s, and, i. Body ratio made ofa resrn
`material containing 80~100% of the porylactic acid -l_- has a thickness or diameter of 10 ~ 500mm. poiylactic acid -L-
`solidified tensile strength at a temperature 66 ( as 5 ~ tOOMPa extrusion molded product is provrded.
`Try the new Googie Patients; with machine-classified Googia Scholar results, and Japanese and South Korean patents.
`
`httpscr'fwww. googlc.com/patentsr’W020 1 41 09347A] ?clficn&dq=W02014109347&h1:en...
`
`10.3’11/2017
`
`
`
`Patent W02014109347A1 - Poly-l-lactic acid solidified and extrusion-molded article, met... Page 5 of 20
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`As aspects of the present invention, resin material. wherein the polylactic acrd ~L- solidified extrudate is poly -L— aCid
`
`composition some,
`j: b: to 70% by weight of filler based on the total quantity is provided .
`
`According to the invention the weight average molecular weight of 100,000 to 380000, the melt viscosity measured at a
`
`temperature 240 ”C and a shear rate of lzosec ‘7 is 20 ~ 2,000Pa > s, and. L body ratio of 80 and to 100% poly ~L— lactic
`acid (to a total volume of 100 mass% of the resin material.) The resin material containing 5 to 70 wt% of the filler in the
`total amount consists of, 10 ~ 500mm have a thickness or diameter of a tensile strength of 5 ~ ZOOMPa at a temperature
`of 66 '(i' poly wL_ lactic acid solidified extrudate is provided
`
`According to the present invention. as a mode of implementation the followrng (i) to polylactic and -L— solidified extrudate
`(is) is provrded.
`{ll filler. wherein the polylactic acid -L— solidified extrudate is fibrous fillers,
`(2) filter, said poly -L- lactic acid solidified extrudate having 100 or more of aspect ratio
`(:3) the resin material for the poly lactic acid —l.- 100 parts by weight, the weight average molecular weight of 100,000 to
`380.000,. the melt viscosdy measured at a temperature 240 ”t‘ and a shear rate of 120sec “l is 20 to a 2,000Pa s, and‘
`the poly --l_~ lactic acid solidified extrudate D body ratio contains poly ~Dv lactic aCid 40-200 parts by weight of 80-10096.
`(4} the poly~lactic add and poly -L- -D~ lactic acid, wherein the poiylactic acid ~L- solidified extrudates which form the
`stereocomplex
`(5} round rod wherein the polylactic acid -L- solidified extrudate havmg the shape of a hollow or a flat,
`
`(6) The poly ~L- lactic cost solic
`l extrudate which is a material for machining.
`
`Furthermore, according to the present invention, the poly ~L- acid solidified extrudate was machined to form the diameter
`of 20 ~ 200mm well drilling ball sealers or well drilling downhole for a material for machining tool member is provided;
`furthermore the sealing plug comprising a downhole tool member for \l\ Drilling is provided.
`
`Further. according to the present invention. sealing with a specific embodiment of the sealing plug with the wellbore drilling
`downhole tool member, the following; {i} well drilling downhole tool member ~ (Xiv) plug is provided.
`{5; the wellbore drilling downhcle tool member,
`a. Mandreit
`b. A pair of rings placed on the outer peripheral surface perpendicular to the axial direction of the mandrel, and:
`c An outer Circumferential surface perpendicular to the axral direction of the mandrel, said sealing plug is at least one
`selected from the group consisting of one or both of the slip or wedge placed in. position between the pair of rings.
`{iii mandrel. said sealing plug having a hollow portion along the axial direction.
`
`mandrel. said sealing plugs ratio of the outer diameter of the hollow portion to the diameter of the mandrel is 0.7 or
`less.
`
`{iv) the mandrel and, said sealing plug is a one ring of a pair of rings are formed integrally
`(V; a mandrel wherein the sealing plug radius of curvature of the working portion of the outer peripheral surface is 0.5mm
`or more.
`
`(\fi) the outer peripheral surface of the mandreil the eyes stop plug having a place that is protected by metal
`{viii on the outer peripheral surface of the mandrel, said of the sealing plug is not provided with the slip and wedge
`Ari outer circumferential surface perpendicular to the axial direction of (will mandrel was placed at a position between the
`pair of rings. said sealing plug comprismg a combination of at least one slip and wedge
`(ix) the slip and the said sealing plug comprising a pluraliiy of combination of the wedge,
`(X; a on the outer peripheral surface perpendicular to the axial direction of the mandrel, one placed at a position between
`the pair of rings, said sealing plug comprising a rubber member of the at least one expandable annular
`(Xi) expandable annular rubber member. the axial length of the mandrel, wherein the sealing plug 10 to 70% the length of
`the mandrel
`
`{Xlii mandrel. said of the sealing plug harm a fixmg portion fixed to remain in the compressed state of the expandable
`annular rubber member of the outer peripheral surface
`(Xsii) a fixed portion: a groove, stepped portions and said sealing plug is at least one selected from the group consisting of
`threads
`
`{Xiv'} expandable annular said of the sealing plug multiple equipped with a rubber member
`
`ln addition. according to the present invention, through the followsng steps 1 to 4.
`1} weight average molecular weight of 150,000 to 540000. temperature 240 “C and a shear rate of lzosec “ in the
`measured melt viscosity of 30 ~ 3.000Pa st and poly-L—body ratio is 80-100% The resin material containing -L~ lactic acid,
`is fed to an extruder and melt-kneaded at a cylinder temperature of 195 ~ 260 “C extruder step 1;
`2) from the extrusion die of the extruder tip, a resin material which is melted by melt-kneading. a channel having a cross—
`sectionai shape of the molten resin passage and communicating and extruded product of the extrusion die, the forming die
`and a cooling; means step of extrusion into the flow channel 32,
`3) i: is solidified by cooling the forming die flow path melt extrudate comprising a resin material then step 3 is extruded
`solidified extrudate to the outSide from the tip of the forming die; a and 4) solidifying the extrudate is pressurized Te, and
`
`receipt while applying back pressure in the forming rile dire: ‘
`a that time. by suppressmg the expansion in the thickness
`Tamer moanmnmmmesmaewnme snaimammmaatew-
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`Patent W02014109347A1 - Poly—l-lactic acid solidified and extrusion-molded article, met... Page 6 of 20
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`to ~ 500mm Step 4;
`Have a thickness or diameter of 10 ~ 500mm. including a method of manufacturing a tensile strength is 5 ~ 100MPa
`polylactic and -L- solidified extrudate at a temperature 66 "C is provided
`
`Desrred by, according to the present invention, the following steps 1 ‘to 4;
`
`ii weight average molecular weight of 150.000 to 540,000, temperature 240 °C and a shear rate of lzosec “ in the
`1
`measured melt viscosrty is 30 ~ 3,000Pa - s and, is a L-isomer ratio is 80-10096 with poly -L- acid. a resin material
`containing 5 to 70 wt% of the fille.r in total amount (the total amount of the resin material is 1.00 wt%.). was fed to an
`extruder. extruder cylinder temperature 195 is melt-kneaded at ~ 260 °C; step 1 i
`2} from the extrusion die of the extruder tip. a resin material which is melted by melt-kneading. a channel having a cross-
`sectional shape of the molten resin passage and communicating and extruded product of the extrusron die. the forming die
`and a cooling means step of extrusion into the flow channel 2:
`3) it is solidified by cooling the forming die flow path melt extrudate cistersrising a resin material. then step 3 is extruded
`solidified extrudate to the outside from tile tip of the forming die; a and 4) solidifying the extrudate is pressurized Te, and
`receipt while applying back pressure in the forming die direction that time. by suppressing the expansron in the thickness
`direction or radial direction of the solidified extrudate by pressure. the thickness or diameter obtain a solidified extrudate of
`10 ~ 500mm Step 4;
`Have a thickness or diameter of 10 ~ 500mm. including a method of manufacturing a tensile strength is 5 ~ 200MPa
`
`polyiactic acrd
`solidifi.
`..e at a temperature 66 “C is providm,
`
`According to the present invention. poly -L- acid solidified extrudate obtained in step 4. the method of manufacturing
`further comprising is provided a process 5 for the heat treatment 3424 hours at a temperature of 90 ~ :90 “1'
`
`Additionally. according to the present invention, by usmg the wells drilled ball sealers. that some or all of the well drilling
`ba=l sealers are decomposed after performing a sealing treatment of the wellbore well dn‘ilsng wherein the, and, using a
`sealing plug prowded with the wellbore drilling downhole tool member, after carrying out the sealing treatment of the
`weilbore. the downhole tool for well drilling well drilling wherein the part of the members or the whole is decomposed is
`provrded.
`
`According to the present invention the weight average molecular weight of “30-0000 to 380.000. the melt viscosity
`measured at a temperature 240 ”C' and a shear rate of 1205ec "
`is 20 ~ 2.000% , s. and. L form proportion There made of
`a resin material containing 801.00% of the polylactic acid -L-, 10 to have a thickness or diameter of 500mm, a tensile
`strength of 5 ~ 100M Pa at a temperature 66 “if; the desired is 5 ~ ZOOMPa poly molding by being -l.~ lactic solidified
`extrudate. cutting. drilling, secondary molded article having a desired shape by mechanical processing such as cutting. in
`particular. the well drilling downhole tool members or the like provided in the sealing plug It is possible to have sufficient
`strength at (temperature environments in excess of 65 ”C‘) envtroriment that exceeds the underground 1.000rn. degradable
`plastic which is capable of forming a downhole tool members such as the desired shape effect tha