WO1997048759A1 - Procede de post-traitement de particules preexpansees de resine polyolefinique - Google Patents
Procede de post-traitement de particules preexpansees de resine polyolefinique Download PDFInfo
- Publication number
- WO1997048759A1 WO1997048759A1 PCT/JP1997/002074 JP9702074W WO9748759A1 WO 1997048759 A1 WO1997048759 A1 WO 1997048759A1 JP 9702074 W JP9702074 W JP 9702074W WO 9748759 A1 WO9748759 A1 WO 9748759A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- foaming agent
- steam
- particles
- polyolefin resin
- combustible
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/3461—Making or treating expandable particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/56—After-treatment of articles, e.g. for altering the shape
- B29C44/5609—Purging of residual gas, e.g. noxious or explosive blowing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
- Y10S264/09—Pre-expansion of foamed polystyrene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S521/918—Physical aftertreatment of a cellular product
Definitions
- the present invention relates to a method for post-processing a polyolefin resin pre-expanded particle. More specifically, the polyolefin resin prefoamed particles foamed with a combustible foaming agent are used to eliminate the risk of spontaneous ignition in the air.
- polyrefin-based resin pre-expanded particles have been used for energy absorbers such as bumpers for automobiles and core materials, as well as for thermal insulation materials.
- energy absorbers such as bumpers for automobiles and core materials
- thermal insulation materials such as thermal insulation materials.
- foams manufactured by in-mold foam molding are used.
- Polyolefin-based resin pre-expanded particles are generally prepared by charging resin particles together with water into a pressure-resistant container, and adding dichlorofluoromethane, dichloromethane, or the like.
- a foaming agent such as roto-tetranole mouth ethane was press-fitted, and the internal pressure of the pressure vessel was increased by heating to increase the internal pressure of the resin particles so that the resin particles contained the foaming agent. That is, they are manufactured by releasing them under atmospheric pressure.
- fluorinated foaming agents diffuse into the air and rise to the stratosphere, destroying the ozone layer and increasing the rate of harmful radiation to the surface, causing skin damage. It is said that there is a risk of causing many diseases such as cancer, and restrictions on its use have been set.
- a foaming agent that replaces the fluorocarbon foaming agent has been For example, aliphatic hydrocarbon gases such as propane, butane, pentane and hexane are being used.
- the produced pre-expanded particles may be left in the air, for example. Then, the aliphatic hydrocarbon-based gas gradually released from inside the pre-expanded particles ignites on the surface of the pre-expanded particles by static electricity or the like, and the pre-expanded particles are ignited. He was always worried about burning up (Japanese Patent Laid-Open No. 61-11539).
- the flammable blowing agent in the pre-expanded particles is replaced with nitrogen gas, carbon dioxide gas, helium gas.
- a post-treatment method of disposing of the foam particles in the air is used. It has been proposed (Japanese Patent Publication No. 7-321, U.S. Pat. No. 4,937,271).
- sparks due to static electricity or the like generated on the surface of the pre-expanded particles ignite the foaming agent discharged from the pre-expanded particles and burn. It is a safer method because it allows you to refill pre-expanded particles without waste.
- the present invention has been made in view of the above-mentioned conventional technology, and it is possible to extract a combustible blowing agent from pre-expanded particles in a short time. It is possible to reuse the extracted combustible foaming agent for the polyolefin resin pre-expanded particles that can be reused. It aims to provide a post-processing method. Disclosure of the invention
- the present invention provides a pre-expanded polyolefin-based resin foamed by using a combustible foaming agent, in an extraction vessel filled with water vapor, and then in the extraction vessel. Water vapor is additionally supplied into the inside, and a combustible foaming agent gas is extracted from the polyrefin-based resin pre-expanded particles, and then the extracted combustible foaming agent gas is extracted.
- the steam contained therein is continuously or intermittently taken out from the extraction container, and the steam is liquefied to separate and collect a combustible blowing agent gas.
- the present invention relates to a post-treatment method for pre-expanded polyolefin resin particles. Brief explanation of drawings
- FIG. 1 is a schematic explanatory view of the post-treatment method for the polyolefin resin pre-expanded particles of the present invention.
- BEST MODE FOR CARRYING OUT THE INVENTION According to the method for post-treatment of pre-expanded polyolefin resin particles of the present invention, as described above, a combustible foaming agent is used.
- the foamed polyolefin resin pre-expanded particles are put into an extraction container filled with water vapor in advance, and then steam is additionally supplied into the extraction container. After extracting a combustible foaming agent gas from the polyolefin resin pre-foaming particles, the extracted steam containing the combustible foaming agent gas is extracted.
- low-density polyolefin is used as the raw material for the polyolefin resin pre-expanded particles used in the present invention.
- the polyrefin-based resin pre-expanded particles may include a nucleating agent such as talc, an ultraviolet absorber, an antistatic agent, and the like. It may be blended with agents, heat stabilizers, flame retardants, coloring agents, fillers, etc.
- a pol- yolefin-based resin cross-linked by, for example, peroxidation or electron beam irradiation is used. You can use it.
- an extruder or a pre-extruder is usually used in order to make the pre-expansion easier. Melting using a goo, rubber mixer, roll, etc., to obtain a desired shape such as a columnar, elliptical columnar, bulbous, cubic, cuboid, etc.
- the particles should be shaped so that the average particle size of the particles is 0.1 to 10 mm, and preferably 0.7 to 5 mm. It is better.
- the method of pre-foaming the polyolefin resin is applied to the polyolefin resin in a pressure vessel.
- flammable blowing agents represented by aliphatic hydrocarbon blowing agents such as butane, butane, pentane and hexane.
- the amount of the flammable foaming agent used there is no particular limitation on the amount of the flammable foaming agent used, and it may be appropriately adjusted according to the expansion ratio of desired pre-expanded particles. It is 5 to 50 parts with respect to 100 parts of the olefin resin (weight part, the same applies hereinafter).
- a dispersing agent calcium tertiary phosphate, basic magnesium carbonate, basic zinc carbonate, calcium carbonate may be used.
- Inorganic dispersants such as um
- surfactants such as dodecylbenzensulfonate soda, n-no, and so on. It is possible to use sodium raffinesulfonate, ⁇ -refrinsulfonate soda and the like.
- the amount of the dispersing agent or surfactant used depends on the type of the resin, the type of the polyolefin resin used, the amount used, and the like. Then, with respect to 100 parts of water, 0.2 to 3 parts with a dispersant and 0.001 to 0.3 parts with a surfactant.
- the polyolefin resin pre-expanded particles containing the flammable foaming agent are usually added to 100 parts of water in order to improve the dispersibility in water. On the other hand, it is preferable to add 20 to 100 parts.
- the polyolefin-based resin-prepared foamed particles containing the flammable foaming agent come into contact with air as described above, and if the foamed particles are on the surface of the pre-foamed particles, static electricity is generated. In the event that sparks are generated, special attention should be paid to the handling of the bow I, which is the one that fires and burns. Therefore, it is preferable that the prepared expanded foam particles be quickly put into the extraction container.
- the piping to the extraction container and the inside of the extraction container may ignite even if sparks due to static electricity or the like are generated on the surface of the pre-expanded particles. It is preferred that they have already been replaced by water vapor in order to avoid them.
- the concentration of oxygen gas in the steam is preferably 5% by volume or less, and from the viewpoint of reusing the flammable blowing agent, the concentration of the oxygen gas in the steam is low.
- the concentration of oxygen gas in the gas is preferably 1% by volume or less.
- the apparatus for producing the pre-expanded particles depends on the extraction container and the piping described above. It is preferable that they are connected.
- the extraction container is a container used for extracting the flammable blowing agent contained in the pre-expanded particles, and is not particularly limited to the extraction container.
- any material that can withstand the pressure and temperature of the steam supplied into the extraction container may be used.
- a specific example of such an extraction container for example, a lower conical cylindrical container made of stainless steel is used.
- the temperature of the steam additionally supplied into the extraction container is lower than the melting point of the raw material resin used for the pre-expanded particles, preferably in a temperature range of 90 to 110 ° C. Hopefully it will be adjusted within.
- the pressure of steam additionally supplied into the extraction container It is desired that the pressure be adjusted so as to be equal to or lower than the saturated water vapor pressure at the melting point of the raw resin of the pre-expanded particles, preferably 0.7 to 1.5 kg Zcm 2 . Yes.
- the flammable foam is generated from the pre-expanded particles in the extraction container.
- the extraction of the agent is preferred in that when the pre-expanded particles are left in the air, they are unlikely to be ignited by static electricity or the like. No.
- the steam containing the combustible blowing agent gas extracted from the preliminary foaming particles is continuously or intermittently extracted from the extraction container to liquefy the steam. Then, the combustible blowing agent gas is separated and collected.
- the water vapor containing the combustible foaming agent gas removed from the extraction container is introduced into, for example, a condenser, and is cooled to 30 ° C or less in the condenser.
- the water can be separated from the flammable blowing agent gas.
- the combustible blowing agent gas separated from water can be reused as a blowing agent, for example, by collecting it in a gas holder or the like. .
- FIG. 1 is a schematic explanatory diagram of a method for post-treatment of a polyolefin resin-prepared foamed particle of the present invention.
- the polyolefin resin preparatory foam particles are produced by the production apparatus 1 and the valve 2 is opened. Thus, it is supplied to the extraction container 3. At this time, before supplying the pre-expanded particles into the extraction container 3, the valve 5 is first opened from the water vapor supply device 4 to extract steam. As described above, it is preferable that the oxygen is introduced into the extraction container 3 and the oxygen concentration in the extraction container 3 is set to 1% by volume or less.
- the valve 2 After supplying the pre-expanded particles into the extraction container 3, the valve 2 is closed, and the combustible foaming agent in the pre-expanded particles is extracted with steam in the extraction container 3.
- the flammable blowing agent After extracting the flammable blowing agent from the pre-expanded particles, the flammable blowing agent is contained in the steam, and the steam containing the flammable blowing agent is The water vapor introduced into the condenser 6 and containing the combustible foaming agent is condensed by cooling to become water. The combustible foaming agent gas separated from the condensed water is collected in the gas holder 17.
- the combustible foaming agent recovered in the gas holder 7 is in a gaseous state or a compressed liquefied liquid state (the compression liquefaction apparatus is omitted in the drawing). In either case, by opening the valve 8, the pre-expanded particles are supplied to the production device 1 for reuse and reused.
- the polyolefin-based resin containing a combustible foaming agent is used. From the pre-expanded particles, the combustible blowing agent can be safely and efficiently extracted. However, since only water can be easily removed from the water vapor containing the combustible foaming agent, the combustible foaming agent can be efficiently recovered and reused. Has the advantage of being able to
- a stainless steel lower conical cylindrical container (capacity 1.6 m 3 ) is used as an extraction container, and a pressure of 1.0 kg Z cm 2 is applied to the extraction container. 0 0.
- the oxygen concentration in the vessel was adjusted to 0.1% by volume by introducing the water vapor of C.
- the oxygen concentration was measured using an oxygen concentration meter (PS-20, manufactured by Shin Kosmos Electric Co., Ltd.). After that, 25 kg of the pre-expanded particles containing the combustible foaming agent, which was produced by the apparatus for producing the polyolefin-based resin pre-expanded particles, was transferred to the extraction container.
- the physical properties of the pre-expanded particles used are as shown in Table 1. Table 1 Physical properties of spare foam particles
- Resin component Ethylene-propylene random copolymer (density: 0.9gZcm3, melt index (Ml): 9.0, ethylene content: 4.5% by weight, vicat softening point: 119 ° C)
- True density ( 30 times expanded particles) 0.03g / cm 3 5kg of flammable blowing agent (isobutane)
- the true density of the pre-expanded particles is determined by measuring the weight (W g) of the pre-expanded particles and submerging the same in water.
- the steam containing the combustible foaming agent obtained in the extraction container is intermittently introduced into the condenser and cooled to 30 ° C to liquefy the steam. Separated from the flammable blowing agent, the flammable blowing agent was recovered with a yield of about 98% or more.
- Example 1 the oxygen concentration in the extraction container was adjusted to 0.1% by volume by replacing the oxygen concentration with nitrogen gas in advance.
- the supply of nitrogen gas at 100 ° C in place of the water vapor at 0 ° C is similar to that in Example 1, except for the use of pre-expanded foam particles. These combustible foaming agents were extracted.
- an activated carbon adsorption device was used to separate and recover flammable gas from nitrogen gas containing a flammable blowing agent obtained in an extraction container.
- the power that could be separated and collected was used.
- Example 2 Using 25 kg of the pre-expanded particles shown in Table 2, the same operation as in Example 1 was performed, and after 20 minutes from the start of the supply of steam, When the concentration of the flammable blowing agent contained in the pre-expanded particles after the passage was examined in the same manner as in Example 1, it was found that 0.1% by weight was obtained.
- the steam containing the combustible foaming agent obtained in the extraction container is intermittently introduced into the condenser and cooled to 30 ° C to liquefy the steam. Separated from the flammable blowing agent, the flammable blowing agent was recovered with a yield of about 98% or more.
- the combustible foaming agent is separated and recovered with high purity from the steam containing the combustible foaming agent obtained in the extraction container. You can see that it can be done.
- the polyolefin resin pre-expanded particles foamed using a flammable foaming agent are used.
- the combustible blowing agent is extracted from the polyolefin resin pre-expanded particles using steam, the steam contained is condensed and liquefied.
- the flammable foaming agent can be separated and recovered with high purity from the water vapor, so that the flammable foaming agent can be reused. Wear .
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Toxicology (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97926262A EP0856547A4 (en) | 1996-06-20 | 1997-06-16 | METHOD FOR TREATING PRE-FOAMED PARTICLES MADE OF POLYOLEFIN RESIN |
US09/000,339 US5821272A (en) | 1996-06-20 | 1997-06-16 | Method for post-treatment of polyolefin resin pre-expanded particles |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16004696 | 1996-06-20 | ||
JP8/160046 | 1996-06-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997048759A1 true WO1997048759A1 (fr) | 1997-12-24 |
Family
ID=15706758
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1997/002074 WO1997048759A1 (fr) | 1996-06-20 | 1997-06-16 | Procede de post-traitement de particules preexpansees de resine polyolefinique |
Country Status (6)
Country | Link |
---|---|
US (1) | US5821272A (ja) |
EP (1) | EP0856547A4 (ja) |
KR (1) | KR100385341B1 (ja) |
CN (1) | CN1065551C (ja) |
MY (1) | MY113656A (ja) |
WO (1) | WO1997048759A1 (ja) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000191860A (ja) * | 1998-12-28 | 2000-07-11 | Kanegafuchi Chem Ind Co Ltd | 含水性ポリプロピレン系樹脂組成物およびそれからなる予備発泡粒子 |
US6245267B1 (en) * | 1999-01-25 | 2001-06-12 | Armacell, Llc | Methods for lowering the density and increasing the flexibility of thermoplastic foams |
AT3797U1 (de) * | 1999-07-13 | 2000-08-25 | Hirsch Maschinenbau Gmbh & Co | Verfahren und vorrichtung zum mehrfachen schäumen von expandierbaren kunststoffen |
JP2001131327A (ja) * | 1999-11-05 | 2001-05-15 | Kanegafuchi Chem Ind Co Ltd | ポリプロピレン系樹脂組成物の型内発泡成形体 |
JP2004228430A (ja) * | 2003-01-24 | 2004-08-12 | Tokyo Seimitsu Co Ltd | 電子ビーム近接露光装置の調整方法および調整装置 |
EP3260261A1 (de) * | 2016-06-23 | 2017-12-27 | Linde Aktiengesellschaft | Hybride vorrichtung zum trocknen und imprägnieren von polymeren granulat zur fertigung von geschäumten kunststoffteilen |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0457838A (ja) * | 1990-06-26 | 1992-02-25 | Kanegafuchi Chem Ind Co Ltd | 熱可塑性樹脂粒子の予備発泡方法およびそれに用いる装置 |
JPH0665481B2 (ja) * | 1991-01-14 | 1994-08-24 | エーエルエー エンマー リサイクリング ウント エントゾルグング ゲゼルシャフト ミット ベシュレンクテル ハフツング イーゲー | 合成発泡体からハロゲン化炭化水素を回収する方法 |
JPH0741595A (ja) * | 1994-02-17 | 1995-02-10 | Kanegafuchi Chem Ind Co Ltd | ポリオレフィン系樹脂予備発泡粒子の後処理法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6151008A (ja) * | 1984-08-21 | 1986-03-13 | Japan Styrene Paper Co Ltd | ポリエチレン系樹脂予備発泡粒子 |
JPH0649795B2 (ja) * | 1985-11-29 | 1994-06-29 | 日本スチレンペ−パ−株式会社 | ポリプロピレン系樹脂予備発泡粒子成型体の製造方法 |
JPH0730201B2 (ja) * | 1988-05-19 | 1995-04-05 | 鐘淵化学工業株式会社 | ポリオレフィン系樹脂予備発泡粒子の後処理法 |
JPH0665481A (ja) * | 1992-08-19 | 1994-03-08 | Kao Corp | ポリエステル樹脂用改質剤、ポリエステル樹脂組成物およびポリエステル樹脂成形品 |
-
1997
- 1997-06-16 KR KR10-1998-0700534A patent/KR100385341B1/ko not_active IP Right Cessation
- 1997-06-16 CN CN97190745A patent/CN1065551C/zh not_active Expired - Fee Related
- 1997-06-16 WO PCT/JP1997/002074 patent/WO1997048759A1/ja not_active Application Discontinuation
- 1997-06-16 US US09/000,339 patent/US5821272A/en not_active Expired - Fee Related
- 1997-06-16 EP EP97926262A patent/EP0856547A4/en not_active Withdrawn
- 1997-06-19 MY MYPI97002754A patent/MY113656A/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0457838A (ja) * | 1990-06-26 | 1992-02-25 | Kanegafuchi Chem Ind Co Ltd | 熱可塑性樹脂粒子の予備発泡方法およびそれに用いる装置 |
JPH0665481B2 (ja) * | 1991-01-14 | 1994-08-24 | エーエルエー エンマー リサイクリング ウント エントゾルグング ゲゼルシャフト ミット ベシュレンクテル ハフツング イーゲー | 合成発泡体からハロゲン化炭化水素を回収する方法 |
JPH0741595A (ja) * | 1994-02-17 | 1995-02-10 | Kanegafuchi Chem Ind Co Ltd | ポリオレフィン系樹脂予備発泡粒子の後処理法 |
Non-Patent Citations (1)
Title |
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See also references of EP0856547A4 * |
Also Published As
Publication number | Publication date |
---|---|
CN1196744A (zh) | 1998-10-21 |
EP0856547A4 (en) | 1998-12-09 |
US5821272A (en) | 1998-10-13 |
KR100385341B1 (ko) | 2003-08-19 |
MY113656A (en) | 2002-04-30 |
KR19990035873A (ko) | 1999-05-25 |
EP0856547A1 (en) | 1998-08-05 |
CN1065551C (zh) | 2001-05-09 |
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