WO2005103128A1 - 樹脂製多孔体およびその製造方法 - Google Patents
樹脂製多孔体およびその製造方法 Download PDFInfo
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- WO2005103128A1 WO2005103128A1 PCT/JP2005/007216 JP2005007216W WO2005103128A1 WO 2005103128 A1 WO2005103128 A1 WO 2005103128A1 JP 2005007216 W JP2005007216 W JP 2005007216W WO 2005103128 A1 WO2005103128 A1 WO 2005103128A1
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- resin
- pore
- forming material
- porous body
- solvent
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- 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
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
- C08J2201/0422—Elimination of an organic solid phase containing oxygen atoms, e.g. saccharose
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- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/044—Elimination of an inorganic solid phase
- C08J2201/0444—Salts
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- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/05—Open cells, i.e. more than 50% of the pores are open
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- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
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- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249954—With chemically effective material or specified gas other than air, N, or carbon dioxide in void-containing component
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249955—Void-containing component partially impregnated with adjacent component
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- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249955—Void-containing component partially impregnated with adjacent component
- Y10T428/249958—Void-containing component is synthetic resin or natural rubbers
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- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
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- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
- Y10T428/249979—Specified thickness of void-containing component [absolute or relative] or numerical cell dimension
Definitions
- the present invention relates to a resinous porous body and a method for producing the same, and more particularly, to a uniform resinous porous body having a uniform communication hole diameter and a uniform distribution of the communication holes, and adding a lubricating oil to the resinous porous body.
- the present invention relates to an impregnated product (hereinafter referred to as a resin-made oil retaining body in the present invention) and a method for producing the same.
- an oil-impregnated resin is obtained by adding a fibrous oil conducting material to an oil-impregnated resin (see Patent Documents 2 to 4) or a mixture of porous silica holding a lubricating oil and a synthetic resin to obtain an oil-impregnated oil.
- a fibrous oil conducting material to an oil-impregnated resin (see Patent Documents 2 to 4) or a mixture of porous silica holding a lubricating oil and a synthetic resin to obtain an oil-impregnated oil.
- Patent Document 5 All of these are designed to continuously supply lubricating oil to the resin surface, and with the aid of conductive materials and porous silica, the amount of lubricating oil in the resin can be increased to about 20% by volume. Has been.
- Patent Document 1 Although a sufficient amount of oil is ensured, the kneading type in which a resin and a lubricant are mixed in advance has a high oil-retaining property, and the use efficiency of the added lubricating oil is low. No. Further, in the case of the kneading type, there is a problem that when the amount of lubricating oil increases, the mechanical strength of the oil-containing resin molded body decreases.
- Patent Literature 2 Patent Literature 3, Patent Literature 4, and Patent Literature 5, as described above, the amount of lubricating oil in the resin is increased to about 20% by volume by the conductive material and porous silica, and Although the mechanical strength can be suppressed by sashimi, if it is applied to a cage of a bearing and lubricated only with oil in the resin, the lubricating oil amount is insufficient and the speed of seepage to the surface is slow. There's a problem.
- Patent Documents 1 to 5 described above are methods for forming a pre-kneaded mixture of resin and lubricating oil into a predetermined shape. Is not applicable.
- Patent Literature 6 and Patent Literature 7 increase the degree of freedom in the combination of resin and lubricating oil, but the resin that can be formed by sintering is limited to ultrahigh molecular weight polyethylene, polyimide resin, etc. .
- the actual porosity is at most 30%, and when applied to bearings of bearings, etc., and lubrication is to be performed only with oil in the resin, the amount of lubricating oil is insufficient. There is a problem that it cannot withstand the recent demand for longer life.
- a desalting method is known as a method for producing a resinous porous body that can adjust the porosity and is inexpensive.
- a molding material obtained by adding a powdery pore-forming material such as sodium chloride or sodium sulfate to resin or rubber is molded into a solid molded body containing the pore-forming material.
- the pore-forming material is eluted by washing with water or the like, and pores are formed in portions where the pore-forming material was present.
- This is a method for producing a porous resin body.
- the porosity is high due to the desalination method.
- a material for producing a porous resinous body As a material for producing a porous resinous body, it is solid at normal temperature, but melts at the molding temperature of the polymer substance that forms the skeleton of the porous resinous body.
- a resin porous body is formed by using a pore-forming material that can exist in a liquid state (see Patent Document 8), and a molding material obtained by dispersing a granular pore-forming material in a polymer substance is used as the porous material.
- Patent Document 9 Molding at a temperature at which a part of the forming material melts, and forming the pores by washing the molded body with a solvent that does not dissolve the polymer substance but dissolves the pore forming material.
- Patent Document 10 there is a method for producing a polyolefin resin porous body having open cells.
- Sodium chloride, salted ammonium, sodium sulfate, sodium nitrate, potassium sulfate, magnesium sulfate, calcium chloride, etc. which are disclosed as pore-forming materials in the above patent documents, are relatively soluble in water. Since it is readily available at low cost and is readily available, it is effective as a pore-forming material used in the production of resin porous bodies having a large pore diameter. It is difficult to completely dissolve and extract the pore-forming material when fine pores are formed while applying force.
- the size of the powdery pore forming material determines the size of the pores. Need to be managed.
- the particle size or material of the pore-forming material it is necessary to classify and control the particle size, and the resin porous body may be expensive.
- Patent Document 1 JP-A-6-41569
- Patent Document 2 JP-A-11 166541
- Patent Document 3 JP-A-2000-71243
- Patent Document 4 JP-A-2000-71244
- Patent Document 5 JP-A-2002-129183
- Patent Document 6 JP-A-61-6429
- Patent Document 7 JP-A-9-76371
- Patent Document 8 Japanese Patent Application Laid-Open No. 2001-2825
- Patent Document 9 Japanese Patent Application Laid-Open No. 2002-194131
- Patent Document 10 JP-A-2002-60534
- Patent Document 11 JP-A-2002-322310
- the present invention has been made to address such a problem, and has a porous body having a high communication porosity and capable of holding a large amount of lubricating oil and the like, and a method of applying lubricating oil to the porous resin body.
- An oil impregnated body made of impregnated oil which has a high oil content and is highly efficient in use of the lubricating oil, and is capable of combining oil and lubricating oil according to the application's specifications. The purpose is to provide oil bodies.
- a resin-made oil retaining body that is used for applications that come into contact with metal parts, etc., and does not allow steel to adhere even if the pore-forming material that is not extracted from the oil retaining body oozes out during use.
- the communication hole in the present invention refers to a hole formed by fusing a plurality of pores without increasing the pore diameter and having a continuous resin surface force.
- the communication porosity in the present invention has substantially the same definition as the porosity described above, and refers to the ratio of the total volume of the communication holes to the resin molded body.
- the resinous porous body of the present invention is a resinous porous body having a communication hole, and the communication hole is formed by molding a resin mixed with a pore-forming material into a molded body. It is a communication hole obtained by extracting the pore-forming material from the molded body using a solvent that dissolves the pore-forming material and does not dissolve the resin.
- the pore forming material is a substance having a melting point higher than the molding temperature of the resin.
- the pore forming material is a water-soluble substance.
- the communicating porosity of the resin porous body is 30% or more.
- the pore-forming material is an alkaline compound.
- the alkaline compound is characterized in that it is at least one metal salt selected from organic alkali metal salts and organic alkaline earth metal salts.
- the alkaline compound is characterized in that it is at least one compound selected from sodium benzoate, sodium acetate, sodium sebacate, sodium triphosphate, sodium pyrophosphate and potassium carbonate.
- the resin porous body is characterized in that the communication holes are impregnated with oil, that is, the resin porous body.
- the oil is a lubricating oil.
- % Or more can be used as lubricating oil.
- the method for producing a resin porous body according to the present invention includes a step of blending a pore-forming material with the resin, a step of molding the resin containing the pore-forming material to form a molded body, Dissolving the forming material and not dissolving the resin; and extracting the pore forming material from the molded body using a solvent.
- the step of blending the pore-forming material with the resin is performed by dissolving the pore-forming material in a solvent in which the pore-forming material is dissolved. Removing the solvent from the liquid to obtain a mixture of the pore-forming material and the resin powder.
- the solvent used in the dispersing step and the solvent used in the step of extracting the pore-forming material are the same solvent.
- the average particle size of the pore-forming material after the solvent removing step is 0.001 ⁇ to 100 / ⁇ m.
- the resin porous body of the present invention has a high communication porosity, and thus can be suitably used for applications such as oil retaining bodies.
- the resin-made oil retaining body obtained by impregnating the above-mentioned resin-made porous body with lubricating oil has a communication porosity of 30% or more, and 60% or more of the total amount of impregnated lubricating oil is used as lubricating oil. As possible, it has excellent oil content and its utilization efficiency, and can provide lubrication for a long period of time. Also, since the molded porous resin body is impregnated with lubricating oil, the lubricating oil must be It can be arbitrarily selected according to the application's specifications without taking into account such factors.
- an alkaline salt which is not an acid salt, particularly an organic alkali metal salt which plays a role of a fireproofing agent, is used, so that iron and steel are present around the material.
- an oil retaining body made of resin is used for a bearing or the like, even if the pore forming material remaining in the oil retaining body oozes out, it is possible to prevent the steel from cracking.
- the method for producing a resin porous body according to the present invention includes a step of mixing a pore-forming material with the resin, a step of molding the resin containing the pore-forming material to form a molded body, A process of dissolving the forming material and not dissolving the resin; and a step of extracting the pore-forming material from the molded body using a solvent.
- a porous body can be manufactured.
- the step of mixing the pore-forming material into the resin comprises, in a solvent in which the pore-forming material is dissolved, a resin powder that is insoluble in the solvent. Since the method includes a dispersion step of dispersing to obtain a dispersion, and a solvent removal step of removing the solvent from the dispersion to obtain a mixture of the pore-forming material and the resin powder, the communication holes having a substantially uniform communication hole diameter are formed. A homogeneous resin porous body having a substantially uniform distribution can be obtained.
- the communication hole diameter in the present invention refers to the hole diameter in a cross section perpendicular to the continuous direction of the holes.
- FIG. 1 is a flowchart of a method for producing a resin porous body according to the present invention.
- FIG. 2 is a view showing the results of a seepage test of an impregnated oil.
- the resin porous body of the present invention is obtained by molding a resin containing a pore-forming material, in particular, an alkaline pore-forming material into a molded body, dissolving the pore-forming material, Dissolve the fat
- the molded body strength is obtained by extracting the pore-forming material using a solvent.
- an organic alkali metal salt or the like as a pore-forming material, even if the pore-forming material is not completely dissolved and extracted, the pore-forming material acts as a gas-proofing agent. It can also be suitably used.
- the most densely packed spheres by point contact include face-centered cubic lattice and hexagonal close-packed packing, and the filling rate is (volume of sphere ⁇ volume of circumscribed cube) ⁇ (height of equilateral triangle) ⁇ bottom
- the communication porosity in the present invention has substantially the same definition as the above porosity, and refers to a porosity in a state where pores are continuous. That is, the ratio of the total volume of pores that are mutually continuous from the resin surface to the resin molded body is as follows.
- the communication porosity was calculated by the method shown in Expression (1) in Equation 1.
- V Volume of the molded body before cleaning molded by the heat compression molding method
- V 2 Volume of pore forming material
- V3 Volume of resin porous body after washing
- V2 Volume of pore-forming material remaining in the resin porous body after washing
- 30% or more, preferably 30% A resin porous body having a communication porosity of about 90%, more preferably about 30 to 70% is obtained.
- the resin porous body usable in the present invention is obtained by molding a resin containing a pore-forming material into a molded body, and then dissolving the pore-forming material and not dissolving the resin. It is obtained by extracting the pore-forming material from the molded body by using the method. For example, a resin A having a molding temperature of X ° C is mixed with a water-soluble powder B having a temperature higher than the temperature of X ° C and a melting point of Y ° C. The water-soluble powder B is extracted from the molded body with water to obtain a resin porous body.
- the method for producing the resinous porous body is not limited to this, and any method that provides a communication porosity of 30% or more can be adopted.
- any method that provides a communication porosity of 30% or more can be adopted.
- FIG. 1 is a flowchart of the manufacturing process.
- the resin powder insoluble in the solvent is dispersed in a solvent in which the pore-forming material is dissolved (SDo dispersion 'mixing is performed until the pore-forming material is completely dissolved.
- the pore forming material is dissolved in the medium, and the dispersion 1 in which the resin powder is dispersed is obtained.
- any solvent can be used as long as it dissolves only the pore-forming material without dissolving the resin powder.
- water and water-soluble solvents such as alcohols, esters, A ketone solvent or the like can be used. Among these, it is appropriately selected according to the above conditions depending on the types of the resin powder and the pore-forming material.
- These solvents may be used alone or in combination of two or more. It is preferable to use water because of its advantages such as easy waste liquid treatment and low cost.
- the liquid solvent is removed from the dispersion liquid 1 obtained in the above step (S1) (S2).
- a mixture 2 of the powdery pore-forming material having a uniform particle size and the resin powder is obtained.
- the mixture 2 becomes a solid such as a powder.
- a method for removing the liquid solvent from the dispersion liquid methods such as heating evaporation, vacuum evaporation, publishing with nitrogen gas, dialysis, and freeze-drying can be used. Since the method is easy and the equipment is inexpensive, it is preferable to remove the liquid solvent by heating and evaporating.
- a method of heating and evaporating if there is no possibility that the dispersion liquid is separated, put the dispersion liquid in a container and put it in a constant temperature bath. It is preferable to use a method of heating while heating.
- the stirrer may be any as long as the submerged mixer is equipped with a heater, or as long as the mixer is installed in a thermostat.
- the mixture 2 from which the liquid solvent has been removed in the above step (S2) is molded according to the intended shape or the like (S3). By this step, a molded article 3 containing the pore-forming material is obtained.
- molding methods such as compression molding, injection molding, extrusion molding, blow molding, vacuum molding, and transfer molding can be adopted.
- the mixture 2 Before molding, the mixture 2 may be processed into pellets, pre-preda and the like in order to improve workability.
- the molded product obtained in the above step (S3) is washed with a solvent that dissolves the pore-forming material to remove the powdery pore-forming material in the molded product (S4).
- a porous resin body 4 having pores in the pore forming material is obtained.
- the powdery pore-forming material is water-soluble, a method of immersing it in warm water of 80 ° C for 10 hours may be used.
- any solvent can be used as long as it dissolves only the pore-forming material without dissolving the resin powder.
- water, an alcohol-based solvent, an ester-based solvent, and a ketone-based solvent can be used as a solvent compatible with water.
- a solvent of the same type as the solvent used in the dispersion step it is preferable to use water because of its advantages such as easy treatment of waste liquid and low cost.
- the liquid solvent When washing with the liquid solvent, the liquid solvent is heated, a plurality of liquid solvents are mixed, or a surfactant is added because the affinity with the pore-forming material is improved and the washing power is improved. Is preferred.
- the liquid solvent can be dissolved and washed in a short time by vibrating the liquid solvent with an ultrasonic cleaner or the like.
- resin powder or pellets such as thermoplastic resin, thermosetting resin, elastomer or rubber can be used.
- the particle size and shape of the resin powder and pellets are not particularly limited in the case of melt molding, since they are kneaded with the pore-forming material during melting. In the case of dry blending and compression molding as it is, it is preferably 1 to 500 / ⁇ .
- thermoplastic or thermosetting resin examples include polyethylene resins such as low-density polyethylene, high-density polyethylene, and ultrahigh-molecular-weight polyethylene, and modified polyethylene.
- Grease water-crosslinked polyolefin resin, polyamide resin, aromatic polyamide resin, polystyrene resin, polypropylene resin, silicone resin, urethane grease, polytetrafluoroethylene resin, black trifluoroethylene Resin, tetrafluoroethylene'hexafluoropropylene copolymer resin, tetrafluoroethylene'perfluoroalkylbutyl ether copolymer resin, bifluoridene fluoride resin, ethylene 'Tetrafluoroethylene copolymer resin, polyacetal resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene ether resin, polycarbonate resin, aliphatic polyketone resin, polybutylpyrrolidone resin, poly Oxazoline resin
- the tensile strength is 49 MPa or more
- the flexural modulus is 1.9 GPa or more
- Engineering resin with heat resistance of 100 ° C or more heat distortion temperature (18.6 kg / cm 2 ;)
- special heat-resistant resin that can be used for a long time even at high temperatures of 150 ° C or more
- super engineering Resins and resins that can be used for industrial applications are preferable because they have particularly excellent mechanical properties or thermal properties such as sliding properties.
- Resins epoxy resins, polytetrafluoroethylene resins, tetrafluoroethylene perfluoroalkyl vinyl ether copolymer resins, unsaturated polyester resins, and ultrahigh molecular weight polyethylene.
- Examples of the elastomer or rubber include acrylonitrile butadiene rubber, isoprene rubber, styrene rubber, butadiene rubber, -tolyl rubber, chloroprene rubber, butyl rubber, acryl rubber, silicone rubber, fluorine rubber, ethylene propylene rubber, and chlorosulfonated rubber.
- Vulcanized rubbers such as polyethylene rubber, chlorinated polyethylene rubber, and epichlorohydrin rubber; Examples thereof include thermoplastic elastomers such as a urethane elastomer, a polyester elastomer, a polyamide elastomer, a polybutadiene elastomer, and a soft nylon elastomer.
- a resin containing the pore-forming material is formed into a molded body, and then the pore-forming material is dissolved, and the resin containing the pore-forming material is dissolved. No Any substance can be used as long as it can also extract resin molding strength using a solvent.
- the pore-forming material is preferably an inorganic salt compound, an organic salt compound, or a mixture thereof, and particularly preferably a water-soluble substance that facilitates the washing and extraction step.
- alkaline substances preferably weakly alkaline substances that can be used as a fire retardant, are preferred.
- the water-soluble pore-forming material include sodium salt sodium, sodium salt ammonium, sodium sulfate, sodium nitrate, potassium sulfate, magnesium sulfate, calcium salt sodium, and thiouric acid.
- a weak alkali salt that can be used as a gas-proofing agent can be preferably used.
- weak alkali salts include organic alkali metal salts, organic alkaline earth metal salts, inorganic alkali metal salts, inorganic alkaline earth metal salts, and the like. It is preferable to use an organic alkali metal salt or an organic alkaline earth metal salt because even when unextracted components fall off, the relatively soft rolling surface and the sliding surface are hardly damaged. These metal salts may be used alone or in combination of two or more. In addition, since inexpensive water can be used as a washing solvent and waste liquid treatment at the time of forming a communication hole becomes easy, it is preferable to use a water-soluble weak alkali salt.
- water-soluble organic alkali metal salt examples include sodium benzoate (melting point 430 ° C), sodium acetate (melting point 320 ° C) or sodium sebacate (melting point 340 ° C), succinic acid Sodium and sodium stearate.
- Sodium benzoate, sodium acetate or sodium sebacate is particularly preferable because it has a high melting point, can cope with various kinds of resins, and has high water solubility.
- Examples of the inorganic alkali metal salt include sodium molybdate, potassium molybdate , Sodium tungstate, sodium triphosphate, sodium pyrophosphate, potassium carbonate and the like.
- the pore-forming material can be used as a mixture of a substance having a melting point higher than the molding temperature of the resin and a substance having a melting point lower than the molding temperature of the resin.
- Examples of the substance having a melting point lower than the molding temperature of the resin include pentaerythritol, boric acid (171 ° C.) and the like.
- the average particle size of the pore-forming material is controlled according to the use of the resin porous body.
- a pore-forming material having an average particle diameter of 1 to 500 m is preferable.
- the pore-forming material is dissolved in order to obtain a homogeneous resinous porous body having a substantially uniform distribution of communication holes having substantially uniform communication hole diameters.
- a resin mixture that is insoluble in the solvent is dispersed in the solvent and the solvent is removed to produce a mixture of the pore former and the resin powder
- the average particle size of the pore former is used.
- the diameter and shape are not particularly limited as long as the solubility in a solvent is sufficient.
- the inexpensive water can be used as a solvent for dissolution or washing, and the waste liquid treatment at the time of pore formation becomes easy, it is preferable to use the above water-soluble substance as the pore forming material.
- the ratio of the pore-forming material is from 30% by volume to 90% by volume, preferably from 40% by volume to 90% by volume, based on the total amount including the resin powder, the pore-forming material and the filler. %. If it is less than 30% by volume, the pores of the resinous porous material are unlikely to become continuous pores. If it is more than 90% by volume, the desired mechanical strength cannot be obtained.
- a filler insoluble in the solvent used for extracting the pore-forming material may be mixed.
- the solvent is water
- glass fibers, carbon fibers and the like may be blended for the purpose of improving the mechanical strength of the porous resin body.
- the method of mixing the resin material and the pore-forming material is not particularly limited, and a kneading method generally used for mixing resins such as dry blending and melt kneading can be applied.
- a method of dissolving a pore-forming material in a liquid solvent to form a transparent solution, dispersing and mixing resin powder in the solution, and then removing the solvent is used.
- the method of dispersing and mixing is not particularly limited as long as it can be mixed in a liquid.
- examples include a ball mill, an ultrasonic disperser, a homogenizer, a juicer mixer, and a Henschel mixer. It is also effective to add a small amount of a surfactant to suppress the separation of the dispersion.
- the resin is mixed with the transparent solution of the pore-forming material, the amount of the solvent is ensured so that the pore-forming material is completely dissolved by the mixing.
- a method for removing the solvent methods such as heating evaporation, vacuum evaporation, nitrogen gas coupling, dialysis, and freeze-drying can be used. It is preferable to remove the liquid solvent by heating and evaporation because the method is easy and the equipment is inexpensive.
- any molding method such as compression molding, injection molding, extrusion molding, blow molding, vacuum molding, transfer molding, etc. can be adopted. Also, to improve workability before molding, it is processed into pellets or pre-preda.
- the extraction of the pore-forming material from the obtained molded body is performed by washing the molded body with a solvent that dissolves the pore-forming material and does not dissolve the resin.
- the solvent for example, water and alcohol-, ester-, and ketone-based solvents that are compatible with water can be used. Among them, it is appropriately selected according to the above conditions depending on the types of the resin and the pore-forming material. These solvents may be used alone or in combination of two or more. Advantages such as easy disposal of waste liquid and low cost It is preferable to use water!
- the oil-retained resin body is obtained by impregnating the above-described porous resin body with a lubricating oil or the like.
- a lubricating oil or the like By using an organic alkali metal salt or the like as the lubricious pore-forming material, even when the pore-forming material is not completely dissolved and extracted, the pore-forming material acts as a fire retardant. It can also be suitably used when there is steel around.
- the oil retaining body made of a resin according to the present invention is excellent in the oil-permissible amount since the communication hole for holding the lubricating oil has a communication hole ratio of 30% or more.
- a communication hole structure that communicates with the oil retaining body surface By having the structure, 60% or more of the total amount of the lubricating oil impregnated can be exuded, so that lubricity can be imparted for a long period of time. The bleeding speed varies depending on the use and use conditions of the oil retaining body made of a resin.
- the lubricating oil to be impregnated is not particularly limited, and mineral oils (paraffin-based, naphthenic-based), synthetic lubricating oils (poly-a-olefin (hereinafter, referred to as PAO), ester oil, cyclopentane) which are generally used are not particularly limited. Oil, fluorine oil (PFPE), silicone oil, and petroleum ether oil). If necessary, a so-called lubricating oil additive such as an antioxidant, an extreme pressure agent, a friction modifier, and an antioxidant may be added.
- the impregnation method may be any method that can impregnate the inside of the resin porous body. After impregnating the resin porous body in an impregnation tank filled with lubricating oil, reduced pressure impregnation is preferably performed. When a high-viscosity silicone oil or the like is used, pressure impregnation can be performed. It is also possible to perform impregnation under pressure and pressure by combining these.
- the cross section of the obtained resin porous body was measured by SEM, and the average particle size and the particle size distribution were measured by using image processing software (SigmaScan Pro: manufactured by SYSTAT Inc.).
- the communication porosity was calculated based on the above equation (1).
- the pore size of the resin porous body evaluated by the above method was 50%, the average diameter of the communication holes was 50 ⁇ m, and the communication holes were uniformly distributed and communicated.
- Comparative Example 1 30.2 g of ultra high molecular weight polyethylene powder (Miperon XM220 manufactured by Mitsui-Danigaku Co., Ltd.) and 69.8 g of sodium salt-dried sodium powder (reagent manufactured by Wako Pure Chemical Industries, Ltd.) were mixed for 5 minutes using a mixer without using a solvent. For a while. The obtained mixed powder was molded by the same heat compression molding method as in Example 1, and the molded body was washed with warm water of 80 ° C by an ultrasonic cleaner to obtain a resin porous body.
- the communicating porosity of the resin-made porous body was 50%, the average diameter of the communicating holes was 500 / zm, the distribution was not uniform, and there was no partial communication. Some parts were seen.
- the sodium chloride powder used had an average particle size of 500 ⁇ m, and the particle size remained unchanged even after the mixing step using a mixer. It is probable that the communication hole diameter of the body was 500 m on average. On the other hand, the pore size of the resin porous body obtained in Example 1 was 50 m on average. This is because, despite the use of the same sodium chloride powder as in Comparative Example 1, the sodium chloride powder was dissolved in water by mixing in water, and the solution was rapidly stirred at a high temperature of 120 ° C. This is probably because the salt was dried and the sodium salt grew to large crystals.
- Ultra high molecular weight polyethylene powder having a volume ratio of 1: 1 (Miperon XM220, manufactured by Mitsui Idani Kagaku Co., Ltd.) and sodium benzoate powder (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed for 5 minutes by a mixer to obtain a mixed powder. Obtained.
- a disk having a diameter of ⁇ 30 and a thickness of t5 mm was formed by a heat compression molding method (200 ° C for 30 minutes). This molded body was washed with warm water of 80 ° C. for 10 hours in an ultrasonic cleaner to elute sodium benzoate powder. Thereafter, drying was performed at 100 ° C for 8 hours to obtain a resin porous body having a communication porosity of 43%. 7% by volume of sodium benzoate was undissolved and remained on the resinous porous body.
- Ultra high molecular weight polyethylene powder having a volume ratio of 1: 1 (Miperon XM220 manufactured by Mitsui Irigaku Co., Ltd.) and sodium acetate powder (reagent manufactured by Wako Pure Chemical Industries, Ltd.) were mixed with a mixer for 5 minutes to obtain a mixed powder.
- a disk having a diameter of ⁇ 30 and a thickness of t5 mm was formed by a heat compression molding method (200 ° C for 30 minutes).
- the molded body was washed with warm water of 80 ° C. for 10 hours using an ultrasonic cleaner to elute sodium acetate powder. Then dry at 100 ° C for 8 hours and communicate A resin porous body having a porosity of 44% was obtained. 6% by volume of sodium acetate was not eluted and remained on the resin porous body.
- a 1: 1 volume ratio of tetrafluoroethylene resin powder (M15, manufactured by Daikin Industries, Ltd.) and sodium benzoate powder (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed for 5 minutes with a mixer to obtain a mixed powder.
- a disk having a diameter of ⁇ 30 and a thickness of 5 mm was formed by a heat compression molding method (350 ° C. ⁇ 30 minutes).
- the molded body was washed with warm water of 80 ° C. for 10 hours using an ultrasonic cleaner to elute sodium benzoate powder. Thereafter, drying was performed at 100 ° C for 8 hours to obtain a resin porous body having a communication porosity of 48%. 2% by volume of sodium benzoate was not eluted and remained on the resinous porous body.
- Ultra high molecular weight polyethylene powder with a volume ratio of 1: 1 (Miperon XM220, manufactured by Mitsui Iri Gaku Co., Ltd.) and sodium salt of sodium salt (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) are mixed with a mixer for 5 minutes to obtain a mixed powder.
- a disk having a diameter of ⁇ 30 and a thickness of 5 mm was formed by a heat compression molding method (200 ° C for 30 minutes). This compact was washed with warm water at 80 ° C. for 10 hours in an ultrasonic cleaner to elute sodium salt powder. Thereafter, drying was performed at 100 ° C for 8 hours to obtain a resin porous body having a communication porosity of 44%. 6% by volume of sodium salt was not eluted and remained on the resin porous body.
- Ultra high molecular weight polyethylene powder having a volume ratio of 1: 1 (Miperon XM220, manufactured by Mitsui Idani Kagaku Co., Ltd.) and pentaerythritol (melting point: 260 ° C, alcohols) were mixed for 5 minutes by a mixer to obtain a mixed powder.
- a disk having a diameter of ⁇ 30 and a thickness of 5 mm was formed by a heat compression molding method (200 ° C for 30 minutes).
- the molded body was washed with warm water of 80 ° C in an ultrasonic cleaner for 10 hours to elute pentaerythritol.
- Ultra high molecular weight polyethylene powder (Miperon XM220, manufactured by Mitsui Chemicals, Inc.) and sodium benzoate powder (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) having a volume ratio of 1: 1 were mixed with a mixer for 5 minutes to obtain a mixed powder. .
- a disk having a diameter of 30 mm and a thickness of 5 mm was molded by a heat compression molding method (200 ° C. for 30 minutes). This molded body was washed with warm water at 80 ° C for 10 hours using an ultrasonic cleaner to elute sodium benzoate powder. Thereafter, drying was performed at 100 ° C.
- Polyphenylene sulfide resin powder with a volume ratio of 2: 1: 1 (D4 Nippon Ink Co., Ltd. Melting point 280 ° C), sodium benzoate powder (Wako Pure Chemical Co., Ltd. reagent, melting point 430 ° C) and pentaerythritol (Wako Pure Chemical Co., Ltd., melting point 260 ° C) mixed for 5 minutes with a mixer
- a mixed powder was obtained.
- a disk having a diameter of ⁇ 30 and a thickness of t5 mm was formed by a heat compression molding method (320 ° C for 30 minutes). The molded body was washed with warm water of 80 ° C.
- Ultra high molecular weight polyethylene powder (Miperon XM220 manufactured by Mitsui Chemicals, Inc.) having a volume ratio of 1: 1 and pentaerythritol (melting point: 260 ° C., alcohols) were mixed by a mixer for 5 minutes to obtain a mixed powder.
- a disk having a diameter of 30 mm and a thickness of 5 mm was molded by a heat compression molding method (200 ° C for 30 minutes). The molded body was washed with warm water at 80 ° C for 10 hours using an ultrasonic cleaner to elute pentaerythritol.
- Ultra high molecular weight polyethylene powder (Miperon XM220 manufactured by Mitsui Chemicals, Inc.) having a volume ratio of 1: 1 and sodium salt powder (reagent manufactured by Wako Pure Chemical Industries, Ltd.) were mixed with a mixer for 5 minutes to obtain a mixed powder.
- a disk having a diameter of 30 mm and a thickness of 5 mm was molded by a heat compression molding method (200 ° C for 30 minutes). This compact was washed with warm water at 80 ° C. for 10 hours using an ultrasonic cleaner to elute sodium salt powder. Thereafter, drying was performed at 100 ° C for 8 hours to obtain a resin porous body having a porosity of 46%.
- the discs prepared in Examples 5 to 8 and Comparative Example 4 were sandwiched between SPCC steel plates (40 ⁇ 40 ⁇ t 2) and subjected to a wet test method (49 ⁇ 1 ° C., relative temperature specified in JISK2246 “rust-proof oil”). (95% or more). After 192 hours (h), 384 hours (h), and 576 hours (h), the appearances of the combined surfaces were compared. Table 2 shows the results.
- Example 5 to 8 and Comparative Example 4 were sandwiched between filter papers, pressed by placing weights thereon, allowed to stand for 100 hours, and then the amount of oil transferred to the filter papers was measured.
- Table 2 shows the ratio of released oil to the total volume of the test piece.
- the oil-made oil retaining body of each of the examples is superior in lubricating property because of excellent oil release property as compared with the comparative example in which grease or oil is mixed.
- sodium chloride Example 8
- Example 8 sodium chloride
- Ultra high molecular weight polyethylene powder (Miperon XM220, manufactured by Mitsui Chemicals, Inc.) and sodium benzoate powder (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) are mixed at a volume ratio of 50:50 using a mixer for 5 minutes. A mixed powder was obtained. Using this mixed powder, a disk having a diameter of 30 mm and a thickness of 5 mm was formed by a heat compression molding method (200 ° C for 30 minutes). The molded body was washed with warm water at 80 ° C for 10 hours using an ultrasonic cleaner to elute sodium benzoate powder. Thereafter, drying was performed at 100 ° C for 8 hours to obtain a resin porous body having a communication porosity of 48%.
- This resin porous body is vacuum impregnated with synthetic lubricating oil (PAO) (Shinfluid 801 manufactured by Nippon Steel Chemical Co., Ltd., viscosity 46 mmVs (40 ° C)) at 60 ° C, and the resin oil is retained for testing. Got a body. The oil content was 45% of the total volume. A bleeding test was performed on the oil retaining body.
- PAO synthetic lubricating oil
- a mixture of tetrafluoroethylene resin powder (Ml 5 manufactured by Daikin Industries, Ltd.) and sodium benzoate powder (reagent manufactured by Wako Pure Chemical Industries, Ltd.) was mixed at a volume ratio of 50:50 using a mixer for 5 minutes.
- a mixed powder was obtained.
- a disk having a diameter of ⁇ 30 mm and a thickness of 5 mm was formed by a calo hot compression molding method (350 ° C for 30 minutes).
- the molded body was washed with warm water of 80 ° C. for 10 hours in an ultrasonic cleaner to elute sodium benzoate powder. Thereafter, drying was performed at 100 ° C for 8 hours to obtain a resin porous body having a communication porosity of 48%.
- This resin porous body was vacuum impregnated with synthetic hydrocarbon oil (Lucant HC-20 (viscosity: 155 mm 2 / s (40 ° C)) manufactured by Mitsui Iridaku Co., Ltd.) at 60 ° C and tested. Oil-retaining body for use in oils. The oil content was 44% of the total volume. A bleeding test of the impregnated oil was performed using this sample.
- synthetic hydrocarbon oil (Lucant HC-20 (viscosity: 155 mm 2 / s (40 ° C)) manufactured by Mitsui Iridaku Co., Ltd.)
- the mixture was melt-kneaded in a ratio by Brabender and then pulverized to obtain a mixed powder.
- a disk having a diameter of 30 mm and a thickness of 5 mm was formed by a heat compression molding method (360 ° C for 30 minutes).
- the compact was washed with warm water at 80 ° C for 10 hours using an ultrasonic cleaner to elute sodium benzoate powder.
- This resin porous body was vacuum impregnated with synthetic lubricating oil (PAO) (Shinfluid 801 manufactured by Nippon Steel Chemical Co., Ltd. (viscosity: 46 mm 2 / s (40 ° C))) at 60 ° C for vacuum testing. ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Obtained oil-made oil retaining body. The oil content was 38% of the total volume. A bleeding test of the impregnated oil was performed using this sample.
- PAO synthetic lubricating oil
- Ultra high molecular weight polyethylene powder (Miperon XM220 manufactured by Mitsui Chemicals, Inc.), polyethylene plex (Santite S, manufactured by Seikagaku Co., Ltd.) and synthetic lubricating oil (PAO) (Shin Fluid 801 manufactured by Nippon Steel Chemical Co., Ltd. mm 2 / s (40 ° C))) and the mixture in a volume ratio of 20:15:65 and put in a mold. Diameter ⁇ 30 mm X thickness t by free sintering method (160 ° C ⁇ 30 minutes) A 5 mm disk was formed. The oil content after molding was 72% based on the total volume. Using this sample, a bleeding test of the impregnated oil was performed.
- the horizontal axis represents the elapsed time (time (h)), and the vertical axis represents the amount of oil reduction (g).
- the resin porous body of the present invention is excellent in water resistance and durability, and therefore, in applications where there is steel around or where long life is required, materials such as cages for rolling bearings and sliding bearings are used. Can be suitably used.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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US11/578,167 US7910198B2 (en) | 2004-04-23 | 2005-04-14 | Resinous porous article and method for production thereof |
EP05730458.6A EP1746125B1 (en) | 2004-04-23 | 2005-04-14 | Porous resin article and method for production thereof |
CN2005800125631A CN1946783B (zh) | 2004-04-23 | 2005-04-14 | 树脂制多孔体及其制造方法 |
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JP2004-128896 | 2004-04-23 | ||
JP2004128897 | 2004-04-23 | ||
JP2004128896 | 2004-04-23 | ||
JP2004-128897 | 2004-04-23 | ||
JP2004132454 | 2004-04-28 | ||
JP2004-132454 | 2004-04-28 | ||
JP2004211030A JP2006028379A (ja) | 2004-07-20 | 2004-07-20 | 多孔質樹脂保油体 |
JP2004-211030 | 2004-07-20 | ||
JP2004379104A JP4206377B2 (ja) | 2004-04-28 | 2004-12-28 | 樹脂製保油体およびその製造方法 |
JP2004-379104 | 2004-12-28 |
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WO2005103128A1 true WO2005103128A1 (ja) | 2005-11-03 |
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PCT/JP2005/007216 WO2005103128A1 (ja) | 2004-04-23 | 2005-04-14 | 樹脂製多孔体およびその製造方法 |
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Country | Link |
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US (1) | US7910198B2 (ja) |
EP (1) | EP1746125B1 (ja) |
CN (1) | CN1946783B (ja) |
WO (1) | WO2005103128A1 (ja) |
Cited By (2)
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WO2007051307A3 (en) * | 2005-11-04 | 2007-06-28 | Ppd Meditech | Porous material and method for fabricating same |
JP2019537636A (ja) * | 2016-10-06 | 2019-12-26 | ソルベイ スペシャルティ ポリマーズ ユーエスエー, エルエルシー | ポリマーと添加剤を含む多孔質物品、それらの調製法およびそれらの使用 |
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JP5033311B2 (ja) * | 2005-03-04 | 2012-09-26 | Ntn株式会社 | 樹脂製保油体およびその製造方法 |
KR100836503B1 (ko) | 2007-05-25 | 2008-06-09 | 서강대학교산학협력단 | 음의 프와송비를 갖는 오목 다공성 구조체 및 그 제조방법 |
WO2009115854A1 (zh) * | 2008-02-21 | 2009-09-24 | Ulvac Inc | 叶片的制造方法 |
US9498922B2 (en) | 2014-06-26 | 2016-11-22 | Vertera, Inc. | Apparatus and process for producing porous devices |
US9504550B2 (en) | 2014-06-26 | 2016-11-29 | Vertera, Inc. | Porous devices and processes for producing same |
WO2016144907A1 (en) * | 2015-03-06 | 2016-09-15 | Wilson John Paul | Instrinsically antimicrobial porosic matrix composites and method of manufacture thereof |
WO2018065526A1 (en) * | 2016-10-06 | 2018-04-12 | Solvay Specialty Polymers Usa, Llc | Porous article comprising a polymer and an additive, processes for their preparation and use thereof |
JP6758156B2 (ja) * | 2016-11-04 | 2020-09-23 | クレハ合繊株式会社 | 分離体、機械要素、運動ガイド装置および産業用機械 |
KR20220062509A (ko) | 2019-09-10 | 2022-05-17 | 솔베이 스페셜티 폴리머즈 유에스에이, 엘.엘.씨. | 다공성 물품, 이의 제조 공정 및 이의 용도 |
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WO2007051307A3 (en) * | 2005-11-04 | 2007-06-28 | Ppd Meditech | Porous material and method for fabricating same |
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JP2019537636A (ja) * | 2016-10-06 | 2019-12-26 | ソルベイ スペシャルティ ポリマーズ ユーエスエー, エルエルシー | ポリマーと添加剤を含む多孔質物品、それらの調製法およびそれらの使用 |
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Also Published As
Publication number | Publication date |
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US7910198B2 (en) | 2011-03-22 |
EP1746125A1 (en) | 2007-01-24 |
EP1746125A4 (en) | 2009-07-22 |
EP1746125B1 (en) | 2016-07-20 |
CN1946783B (zh) | 2012-01-25 |
CN1946783A (zh) | 2007-04-11 |
US20080032112A1 (en) | 2008-02-07 |
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