WO2020194616A1 - Lubricant, powdered mixture, and method for producing sintered body - Google Patents
Lubricant, powdered mixture, and method for producing sintered body Download PDFInfo
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- WO2020194616A1 WO2020194616A1 PCT/JP2019/013415 JP2019013415W WO2020194616A1 WO 2020194616 A1 WO2020194616 A1 WO 2020194616A1 JP 2019013415 W JP2019013415 W JP 2019013415W WO 2020194616 A1 WO2020194616 A1 WO 2020194616A1
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- lubricant
- acid amide
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- powder
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
- C10M105/68—Amides; Imides
Definitions
- the present invention relates to a method for producing a lubricant, a powder mixture and a sintered body.
- Lubricants are usually used for lubrication, for example, to reduce friction between solids in contact.
- examples of the lubricant include liquid lubricating oil, semi-solid grease, solid lubricant and the like.
- a powdery solid lubricant (powdered lubricant) is used.
- the powder mixture is a mixture of an iron-based powder, which is a main raw material powder, an auxiliary raw material powder such as copper powder, graphite powder, and machinability improving powder, and a lubricant powder.
- the lubricant powder By adding a powdery lubricant to the powder mixture, powder characteristics such as fluidity and consolidation in the powder mixture are improved, and the compression-molded green compact can be easily extracted from the mold.
- the lubricant powder include metal soap-based lubricants such as stearic acid and its metal salts, organic lubricants (wax-based lubricants), fatty acid amide-based lubricants, and metal soap-based lubricants and fatty acid amide-based lubricants.
- examples include a mixture with a lubricant (see, for example, Patent Documents 1 and 2).
- the lubricant is compatible with metal powder, powder characteristics when made into a powder mixture, extractability of green compact after compression molding, and dissipative property of lubricant when sintering green compact. Be selected. Among them, zinc stearate is widely used as a lubricant because of its relatively excellent lubricating properties and cost. Such a lubricant is generally used by being mixed in advance with the powder mixture. There is also a method of applying a lubricant to the wall surface of the mold, but since a special device is required, the manufacturing cost of the sintered body becomes relatively high.
- metal soap-based lubricants typified by zinc stearate have a problem of contaminating the product surface, exhaust duct, etc. when sintering green compacts, and are used as organic lubricants (wax-based lubricants). Is desired to be replaced.
- organic lubricant in addition to the lubricants described in Patent Documents 1 and 2, amide compounds having a long-chain alkyl group have been proposed (see, for example, Patent Document 3).
- the powder mixture preferably has high fluidity and preferably has a high density of compaction when formed into a molded product.
- a lubricant containing a lubricant A which is a compound in which at least one monovalent organic group having at least one hydroxy group is bonded to a nitrogen atom of an amide bond.
- the lubricant A according to ⁇ 1> which contains a compound represented by the following general formula (1).
- R 1 is a monovalent organic group having at least one hydroxy group
- R 2 is a monovalent organic group having at least one hydroxy group or a hydrogen atom
- R 3 is. It is a monovalent organic group.
- R 1 is a hydroxyalkyl group having 1 to 3 carbon atoms
- R 2 is a hydrogen atom
- R 3 is a hydrocarbon group having 10 to 30 carbon atoms or a hydrocarbon group having 10 to 30 carbon atoms substituted with at least one hydroxy group.
- ⁇ 5> The lubricant according to any one of ⁇ 1> to ⁇ 4>, wherein the lubricant A contains at least one of methylolstearic acid amide and methylolbehenic acid amide.
- ⁇ 6> The lubricant according to any one of ⁇ 1> to ⁇ 5>, which contains a lubricant B having a melting point lower than that of the lubricant A.
- ⁇ 7> The lubricant according to ⁇ 6>, wherein the lubricant B has a melting point of 60 ° C. to 80 ° C.
- the lubricant B includes oleic acid amide, erucic acid amide, ricinoleic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stealic acid amide, N-stearyl erucate amide, and N.
- the lubricant according to ⁇ 6> above which comprises at least one selected from the group consisting of -oleyl palmitate amide, N-oleyl-hydroxystearic amide, stearic acid, and N-oleyl palmitamide.
- the mass ratio of the lubricant A to the lubricant B is one of the above ⁇ 6> to ⁇ 9>, which is 1: 9 to 9: 1.
- ⁇ 11> The lubricant according to any one of ⁇ 6> to ⁇ 10>, wherein the total content of the lubricant A and the lubricant B with respect to the total amount of the lubricant is 50% by mass to 100% by mass. .. ⁇ 12>
- ⁇ 15> A method for producing a sintered body, which produces a sintered body by sintering the powder mixture according to ⁇ 13> or ⁇ 14>.
- a lubricant capable of improving the fluidity and compaction property of a powder mixture, a powder mixture containing the same, and a method for producing a sintered body using the powder mixture.
- the present invention is not limited to the following embodiments.
- the components including element steps and the like are not essential unless otherwise specified.
- the numerical range indicated by using "-" in the present disclosure indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
- the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. ..
- each component may contain a plurality of applicable substances.
- the content rate or content of each component means the total content rate or content of the plurality of substances unless otherwise specified.
- a plurality of types of particles corresponding to each component may be contained.
- the particle size of each component means a value for a mixture of the plurality of types of particles unless otherwise specified.
- the hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
- the hydrocarbon group may be linear, branched, or include a ring structure.
- the lubricants of the present disclosure include lubricant A, which is a compound in which at least one monovalent organic group having at least one hydroxy group is bonded to an amide-bonded nitrogen atom.
- lubricant A is a compound in which at least one monovalent organic group having at least one hydroxy group is bonded to an amide-bonded nitrogen atom.
- the lubricant of the present disclosure is preferably used for powder metallurgy, for example.
- the scope of the present invention also includes the use of compounds in which at least one monovalent organic group having at least one hydroxy group is bonded to the nitrogen atom of the amide bond for lubricating the powder mixture.
- the lubricant A may be a compound in which at least one monovalent organic group having at least one hydroxy group is bonded to the nitrogen atom of the amide bond.
- the lubricant A one type may be used alone, or two or more types may be used in combination.
- the monovalent organic group having at least one hydroxy group is preferably a hydroxyalkyl group having 1 to 3 carbon atoms, more preferably a methylol group or an ethylol group, and preferably a methylol group. More preferred.
- Lubricant A is preferably a compound in which a monovalent organic group is bonded to a carbon atom constituting an amide-bonded carbonyl group.
- the monovalent organic group bonded to the carbon atom constituting the carbonyl group of the amide bond is a hydrocarbon group having 10 to 30 carbon atoms or a hydrocarbon group having 10 to 30 carbon atoms substituted with at least one hydroxy group. It is preferably a hydrocarbon group having 10 to 30 carbon atoms, and further preferably a hydrocarbon group having 15 to 25 carbon atoms.
- the monovalent organic group bonded to the carbon atom constituting the carbonyl group of the amide bond is a hydrocarbon group having 10 to 30 carbon atoms, the polarity balance of the lubricant is better when added to the powder mixture. Therefore, the fluidity and compactness of the powder mixture tend to be better.
- Lubricant A preferably contains a compound represented by the following general formula (1).
- R 1 is a monovalent organic group having at least one hydroxy group
- R 2 is a monovalent organic group having at least one hydroxy group or a hydrogen atom
- R 3 is 1. It is a valent organic group.
- the monovalent organic group having at least one hydroxy group in R 1 and R 2 is preferably a monovalent organic group having one hydroxy group independently, preferably carbon. It is more preferably a hydroxyalkyl group of the number 1 to 3, further preferably a methylol group or an ethylol group, and particularly preferably a methylol group.
- R 2 is preferably a hydrogen atom
- R 1 is a hydroxyalkyl group having 1 to 3 carbon atoms
- R 2 is more preferably a hydrogen atom
- R 3 is preferably a hydrocarbon group having 10 to 30 carbon atoms or a hydrocarbon group having 10 to 30 carbon atoms substituted with at least one hydroxy group, and preferably a hydrocarbon group having 10 to 30 carbon atoms. More preferably, it is a hydrocarbon group having 15 to 25 carbon atoms.
- the at least one hydrocarbon group having 10 to 30 carbon atoms hydroxy group is substituted at the R 3, may be a group in which one hydroxy group is substituted, a group in which two or more hydroxy groups substituted May be good.
- the lubricant A preferably contains a methylol fatty acid amide, and more preferably contains a methylol fatty acid amide in which a hydrocarbon group having 11 to 21 carbon atoms is bonded to a carbon atom constituting the carbonyl group of the amide bond. It is more preferable to contain at least one of palmitate amide, methylol stearate amide and methylol bechenic acid amide, and particularly preferably to contain at least one of methylol stearate amide and methylol bechenic acid amide. It is even more preferable to include it.
- the lubricant A may be the above-mentioned methylol fatty acid amide, and at least a monovalent organic group having at least one hydroxy group other than the above-mentioned methylol fatty acid amide and the methylol fatty acid amide is added to the nitrogen atom of the amide bond. It may be a mixture with one bound compound.
- the melting point of the lubricant A is preferably 90 ° C. to 140 ° C. from the viewpoint of increasing the fluidity of the powder mixture and the extractability of the molded product.
- the melting point is a value measured by differential scanning calorimetry (DSC).
- the lubricant of the present disclosure preferably contains a lubricant B having a melting point lower than that of the lubricant A.
- a lubricant B having a melting point lower than that of the lubricant A.
- the melting point of the lubricant B is preferably 60 ° C to 80 ° C.
- the lubricant B is oleic acid amide, erucic acid amide, ricinoleic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stealic acid amide, N-stearyl erucic acid amide, N-oleyl palmitic acid. It preferably contains at least one selected from the group consisting of amides, N-oleyl-hydroxystearic amides, stearic acids, and N-oleyl palmitoamides, preferably ricinolic acid amides, stearic acids, oleic acid amides and N-.
- it comprises at least one selected from the group consisting of oleyl palmitoamide.
- it is more preferable to contain N-oleyl palmitoamide from the viewpoint of fluidity and compaction of the powder mixture and extractability of the molded product.
- the mass ratio of the lubricant A to the lubricant B (lubricant A: lubricant B) is 1: 9 to 9: 1 from the viewpoint of the balance between the fluidity and compaction of the powder mixture and the extractability of the molded product. It is preferably 2: 8 to 8: 2, and even more preferably 3: 7 to 7: 3.
- the total content of the lubricant A and the lubricant B with respect to the total amount of the lubricant is preferably 50% by mass to 100% by mass. Further, the total content of the lubricant A and the lubricant B may be 60% by mass to 95% by mass, or 80% by mass to 90% by mass.
- the lubricant A is a methylol fatty acid amide and the lubricant B is N-oleyl palmitoamide.
- the balance between the fluidity and compaction of the powder mixture and the extractability of the molded product tends to be excellent.
- the lubricant of the present disclosure may contain a lubricant other than the lubricant A and the lubricant B.
- examples of other lubricants include amide-based lubricants other than lubricant A and lubricant B.
- one type may be used alone, or two or more types may be used in combination.
- Examples of the amide-based lubricant other than the lubricant A and the lubricant B include fatty acid amide and fatty acid bisamide, which have a higher melting point than the lubricant B.
- fatty acid amide examples include lauric acid amide, partiminic acid amide, stearic acid amide, bechenic acid amide, hydroxystearic acid amide, N-lauryl lauric acid amide, N-palmityl palmitate amide, N-stearyl stealic acid amide, and N-.
- fatty acid amide examples include lauric acid amide, partiminic acid amide, stearic acid amide, bechenic acid amide, hydroxystearic acid amide, N-lauryl lauric acid amide, N-palmityl palmitate amide, N-stearyl stealic acid amide, and N-.
- stearyl-hydroxystearic acid amide examples include lauric acid amide, partiminic acid amide, stearic acid amide, bechenic acid amide, hydroxystearic acid amide, N-lauryl lauric acid amide, N-palmityl palmitate amide, N-stearyl stealic acid
- fatty acid bisamide examples include methylene bisstearic acid amide, methylene bislauric acid amide, methylene bishydroxystearic acid amide, ethylene biscaprylic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, and ethylene bisstearic acid amide.
- the content of the other lubricant with respect to the total amount of the lubricant may be more than 0% by mass and 50% by mass or less, 5% by mass to 40% by mass, or 10% by mass to 20% by mass. May be good.
- the powder mixture of the present disclosure includes a raw material powder and the above-mentioned lubricant of the present disclosure. This powder mixture is excellent in fluidity and consolidation.
- the powder mixture of the present disclosure is preferably used, for example, for powder metallurgy.
- the raw material powder examples include a main raw material powder containing iron as a main component, an auxiliary raw material powder for improving the characteristics of the sintered body, and the like.
- the fact that iron is contained as a main component means that the iron content in the raw material powder is 50% by mass or more of the total raw material powder.
- the main raw material powder examples include pure iron powder that can contain unavoidable impurities (oxygen, silicon, carbon, manganese, etc.) and iron-based powder such as iron-based alloy powder.
- the main raw material powder one type may be used alone, or two or more types may be used in combination.
- the average particle size of the main raw material powder is preferably 30 ⁇ m to 150 ⁇ m, more preferably 50 ⁇ m to 100 ⁇ m.
- the average particle size is the particle size (D50) when the cumulative amount from the small diameter side is 50% in the volume-based particle size distribution measured by the laser diffraction method.
- the iron-based powder can be produced, for example, by a method in which molten iron or a molten iron alloy is made into fine particles by an atomizing method, reduced, and then pulverized.
- the auxiliary raw material powder is not particularly limited as long as it is a raw material powder that can improve the characteristics of the sintered body, and is a powder that improves mechanical properties such as hardness and toughness of the sintered body, and a cover of the sintered body. Examples include powders that enhance shaving properties.
- auxiliary raw material powder examples include metal powders and inorganic powders other than the main raw material powder.
- the auxiliary raw material powder one type may be used alone, or two or more types may be used in combination.
- metal powder examples include powders of copper, nickel, chromium, molybdenum, tin, vanadium, manganese and the like.
- Examples of the inorganic powder include sulfides such as manganese sulfide and manganese disulfide; nitrides such as boron nitride; oxides such as boric acid, magnesium oxide, potassium oxide and silicon oxide; graphite such as natural graphite and artificial graphite; phosphorus; Examples include powders such as sulfur.
- the average particle size of the auxiliary raw material powder is preferably 2 ⁇ m to 100 ⁇ m, and more preferably 5 ⁇ m to 50 ⁇ m.
- the content of the main raw material powder is preferably 90 parts by mass to 99 parts by mass, and more preferably 95 parts by mass to 98 parts by mass.
- the content of the auxiliary raw material powder is preferably 1 part by mass to 10 parts by mass, and more preferably 2 parts by mass to 5 parts by mass.
- the content of the lubricant is preferably 0.1 part by mass to 2.0 part by mass, and more preferably 0.2 part by mass to 1.5 part by mass with respect to 100 parts by mass of the raw material powder. , 0.3 parts by mass to 1.0 part by mass is more preferable.
- the powder mixture of the present disclosure may contain a raw material powder and other components other than the lubricant of the present disclosure.
- Other components include binders. Since the powder mixture contains a binder, segregation, scattering, etc. of the raw material powder tend to be suppressed.
- the binder is not particularly limited, and examples thereof include polyolefin, acrylic resin, polystyrene, styrene-butadiene rubber, ethylene glycol distearate, epoxy resin, rosin ester, and the like.
- the content of the binder is preferably 0.01 part by mass to 1.0 part by mass, and 0.1 part by mass to 1 part by mass with respect to 100 parts by mass of the raw material powder. More preferably, it is 0.0 parts by mass.
- the powder mixture of the present disclosure is obtained by mixing the raw material powder, the lubricant of the present disclosure, and other components as needed.
- the raw material powder and the lubricant of the present disclosure can be mixed by using a commonly used mixer such as a bladed mixer, a V-shaped mixer, or a bicone mixer (W cone). ..
- the method for producing a sintered body of the present disclosure is a method of producing a sintered body by sintering the powder mixture of the present disclosure.
- the method for producing a sintered body of the present disclosure preferably comprises filling a mold with the powder mixture of the present disclosure, compression molding the powder mixture filled in the mold to obtain a molded product, and the like. It includes sintering the molded product extracted from the mold.
- the powder mixture of the present disclosure is excellent in fluidity, the powder mixture of the present disclosure is excellent in filling property into a mold, and a sintered body can be efficiently produced. Since the powder mixture of the present disclosure is excellent in compactness, the density of the molded product obtained by compression molding can be increased, and a sintered body having excellent mechanical properties such as strength can be produced. Further, in the method for producing a sintered body of the present disclosure, when the powder mixture of the present disclosure contains a lubricant B, the pressure when the molded product of the powder mixture is taken out from the mold can be reduced.
- the powder mixture filled in the mold may be compression molded.
- the molding temperature, molding pressure and the like are not particularly limited, and may be appropriately adjusted depending on the composition of the powder mixture, the amount of addition, the shape in the mold and the like.
- a sintered body is manufactured by sintering a powder mixture, and preferably a sintered body is manufactured by sintering a molded body extracted from a mold.
- the conditions for sintering the powder mixture or the molded product are not particularly limited, and a normal sintering method can be adopted.
- Examples 1 to 40 and Comparative Examples 1 to 60 As the main raw material powder, atomized iron powder for powder metallurgy having an average particle size of 75 ⁇ m, electrolytic copper powder having an average particle size of 30 ⁇ m, and graphite powder having an average particle size of 10 ⁇ m were prepared as auxiliary raw material powders. Next, with respect to 97.5 parts by mass of iron powder, 1.5 parts by mass of copper powder, and 1.0 part by mass of graphite powder, lubricant A or other lubricants shown in Tables 1 to 5 and the following, and lubricants. 0.8 parts by mass of the lubricant mixture of B was added.
- Fluidity of powder mixture The fluidity of the powder mixture obtained in each Example and each Comparative Example was evaluated by the fluidity test method specified in JIS Z 2502 (2012).
- the evaluation criteria are as follows. -Evaluation criteria- A powder mixture flowed within 30 seconds. B The powder mixture flowed over 30 seconds and within 35 seconds. C The powder mixture did not flow, or the powder mixture flowed in more than 35 seconds. The results are shown in Tables 1-5. If it is evaluation A or evaluation B, the fluidity of the powder mixture is good.
- the extractability of the cylindrical molded product in each of the examples and the comparative examples is based on the following criteria by measuring the extraction pressure when the cylindrical molded product used for evaluating the compaction property of the powder mixture described above is extracted from the mold. Evaluated. -Evaluation criteria- A Extraction pressure was 8 MPa or less. B The extraction pressure was more than 8 MPa and less than 15 MPa. The C extraction pressure was more than 15 MPa. The results are shown in Tables 1-5. If the evaluation is A or B, the extraction property of the cylindrical molded product is good.
- the powder mixture of Examples 1 to 40 was superior in fluidity and compaction as compared with the powder mixture of Comparative Examples 1 to 60. Further, the powder mixture of Examples 1 to 40 was also good in extractability.
Abstract
This lubricant contains lubricant A, which is a compound in which at least one monovalent organic group having at least one hydroxy group is bonded to the nitrogen atom of an amide bond.
Description
本発明は、潤滑剤、粉末混合物及び焼結体の製造方法に関するものである。
The present invention relates to a method for producing a lubricant, a powder mixture and a sintered body.
通常、潤滑剤は潤滑のために使用され、例えば、接する固体同士の摩擦を軽減するために用いられる。潤滑剤としては、液体の潤滑油、半固形のグリース、固体の潤滑剤等が挙げられ、例えば、粉末冶金法では、粉末状である固体の潤滑剤（粉末状の潤滑剤）が用いられる。
Lubricants are usually used for lubrication, for example, to reduce friction between solids in contact. Examples of the lubricant include liquid lubricating oil, semi-solid grease, solid lubricant and the like. For example, in the powder metallurgy method, a powdery solid lubricant (powdered lubricant) is used.
粉末冶金法のうち、特に金型成形法においては、金型壁面と圧粉体との摩擦を軽減するため、通常、粉末状の潤滑剤を混入させた粉末混合物を用いる。粉末混合物は、主原料粉末である鉄基粉末に、例えば、銅粉末、黒鉛粉末、切削性改善用粉末等の副原料粉末と潤滑剤の粉末とを混合したものである。
Among the powder metallurgy methods, especially in the mold forming method, in order to reduce the friction between the mold wall surface and the green compact, a powder mixture mixed with a powdery lubricant is usually used. The powder mixture is a mixture of an iron-based powder, which is a main raw material powder, an auxiliary raw material powder such as copper powder, graphite powder, and machinability improving powder, and a lubricant powder.
粉末状の潤滑剤を粉末混合物に添加することにより、粉末混合物における流動性、圧密性等の粉末特性が改善され、圧縮成形した圧粉体が金型から抜き出し易くなる。潤滑剤の粉末としては、例えば、ステアリン酸及びその金属塩等の金属石鹸系潤滑剤、有機系潤滑剤（ワックス系潤滑剤）、脂肪酸アミド系潤滑剤、並びに金属石鹸系潤滑剤と脂肪酸アミド系潤滑剤との混合物が挙げられる（例えば、特許文献１及び２参照）。
By adding a powdery lubricant to the powder mixture, powder characteristics such as fluidity and consolidation in the powder mixture are improved, and the compression-molded green compact can be easily extracted from the mold. Examples of the lubricant powder include metal soap-based lubricants such as stearic acid and its metal salts, organic lubricants (wax-based lubricants), fatty acid amide-based lubricants, and metal soap-based lubricants and fatty acid amide-based lubricants. Examples include a mixture with a lubricant (see, for example, Patent Documents 1 and 2).
潤滑剤は、金属粉末との混合性、粉末混合物としたときの粉末特性、圧縮成形後の圧粉体の抜き出し性、圧粉体を焼結する際の潤滑剤の逸散性等の点から選択される。中でも、比較的優れた潤滑特性及びコストの点から、ステアリン酸亜鉛が潤滑剤として広く用いられている。このような潤滑剤は、粉末混合物に予め混入させて用いるのが一般的である。なお、潤滑剤を金型壁面に塗布して用いる方法もあるが、特殊な装置が必要となるため、焼結体の製造コストが割高となる。
The lubricant is compatible with metal powder, powder characteristics when made into a powder mixture, extractability of green compact after compression molding, and dissipative property of lubricant when sintering green compact. Be selected. Among them, zinc stearate is widely used as a lubricant because of its relatively excellent lubricating properties and cost. Such a lubricant is generally used by being mixed in advance with the powder mixture. There is also a method of applying a lubricant to the wall surface of the mold, but since a special device is required, the manufacturing cost of the sintered body becomes relatively high.
しかしながら、ステアリン酸亜鉛に代表される金属石鹸系潤滑剤は、圧粉体を焼結する際に製品表面、排気ダクト等を汚染するという問題があり、有機系潤滑剤（ワックス系潤滑剤）への置き換えが望まれている。有機系潤滑剤としては、特許文献１及び２に記載された潤滑剤のほか、長鎖アルキル基を有するアミド系化合物が提案されている（例えば、特許文献３参照）。
However, metal soap-based lubricants typified by zinc stearate have a problem of contaminating the product surface, exhaust duct, etc. when sintering green compacts, and are used as organic lubricants (wax-based lubricants). Is desired to be replaced. As the organic lubricant, in addition to the lubricants described in Patent Documents 1 and 2, amide compounds having a long-chain alkyl group have been proposed (see, for example, Patent Document 3).
有機系潤滑剤を粉末混合物の添加剤として用いる場合であっても、粉末混合物は高い流動性を有することが好ましく、成形体としたときに高密度となる圧密性を有することが好ましい。
Even when an organic lubricant is used as an additive for the powder mixture, the powder mixture preferably has high fluidity and preferably has a high density of compaction when formed into a molded product.
本開示は、粉末混合物の流動性及び圧密性を向上させることができる潤滑剤、これを含む粉末混合物並びに粉末混合物を用いた焼結体の製造方法を提供することを目的とする。
It is an object of the present disclosure to provide a lubricant capable of improving the fluidity and compaction property of a powder mixture, a powder mixture containing the same, and a method for producing a sintered body using the powder mixture.
前記課題を達成するための具体的手段は以下の通りである。
＜１＞ 少なくとも１つのヒドロキシ基を有する１価の有機基がアミド結合の窒素原子に少なくとも１つ結合した化合物である潤滑剤Ａを含む潤滑剤。
＜２＞ 前記潤滑剤Ａは、下記の一般式（１）で表される化合物を含む前記＜１＞に記載の潤滑剤。 Specific means for achieving the above-mentioned problems are as follows.
<1> A lubricant containing a lubricant A, which is a compound in which at least one monovalent organic group having at least one hydroxy group is bonded to a nitrogen atom of an amide bond.
<2> The lubricant A according to <1>, which contains a compound represented by the following general formula (1).
＜１＞ 少なくとも１つのヒドロキシ基を有する１価の有機基がアミド結合の窒素原子に少なくとも１つ結合した化合物である潤滑剤Ａを含む潤滑剤。
＜２＞ 前記潤滑剤Ａは、下記の一般式（１）で表される化合物を含む前記＜１＞に記載の潤滑剤。 Specific means for achieving the above-mentioned problems are as follows.
<1> A lubricant containing a lubricant A, which is a compound in which at least one monovalent organic group having at least one hydroxy group is bonded to a nitrogen atom of an amide bond.
<2> The lubricant A according to <1>, which contains a compound represented by the following general formula (1).
（一般式（１）中、Ｒ１は少なくとも１つのヒドロキシ基を有する１価の有機基であり、Ｒ２は少なくとも１つのヒドロキシ基を有する１価の有機基又は水素原子であり、Ｒ３は１価の有機基である。）
＜３＞ Ｒ１は炭素数１～３のヒドロキシアルキル基であり、Ｒ２は水素原子である前記＜２＞に記載の潤滑剤。
＜４＞ Ｒ３は、炭素数１０～３０の炭化水素基又は少なくとも１つのヒドロキシ基が置換した炭素数１０～３０の炭化水素基である前記＜２＞又は＜３＞に記載の潤滑剤。
＜５＞ 前記潤滑剤Ａは、メチロールステアリン酸アミド及びメチロールベヘン酸アミドの少なくとも一方を含む前記＜１＞～＜４＞のいずれか１つに記載の潤滑剤。
＜６＞ 前記潤滑剤Ａよりも融点が低い潤滑剤Ｂを含む前記＜１＞～＜５＞のいずれか１つに記載の潤滑剤。
＜７＞ 前記潤滑剤Ｂの融点が６０℃～８０℃である前記＜６＞に記載の潤滑剤。
＜８＞ 前記潤滑剤Ｂは、オレイン酸アミド、エルカ酸アミド、リシノール酸アミド、Ｎ－オレイルオレイン酸アミド、Ｎ－ステアリルオレイン酸アミド、Ｎ－オレイルステアリン酸アミド、Ｎ－ステアリルエルカ酸アミド、Ｎ－オレイルパルミチン酸アミド、Ｎ－オレイル－ヒドロキシステアリン酸アミド、ステアリン酸、及びＮ－オレイルパルミトアミドからなる群より選択される少なくとも１つを含む前記＜６＞に記載の潤滑剤。
＜９＞ 前記潤滑剤Ｂは、Ｎ－オレイルパルミトアミドを含む前記＜６＞に記載の潤滑剤。
＜１０＞ 前記潤滑剤Ａと前記潤滑剤Ｂとの質量比（潤滑剤Ａ：潤滑剤Ｂ）は、１：９～９：１である前記＜６＞～＜９＞のいずれか１つに記載の潤滑剤。
＜１１＞ 潤滑剤全量に対する前記潤滑剤Ａ及び前記潤滑剤Ｂの合計の含有率は、５０質量％～１００質量％である前記＜６＞～＜１０＞のいずれか１つに記載の潤滑剤。
＜１２＞ 粉末冶金に用いる前記＜１＞～＜１１＞のいずれか１つに記載の潤滑剤。
(In the general formula (1), R 1 is a monovalent organic group having at least one hydroxy group, R 2 is a monovalent organic group having at least one hydroxy group or a hydrogen atom, and R 3 is. It is a monovalent organic group.)
<3> The lubricant according to <2> above, wherein R 1 is a hydroxyalkyl group having 1 to 3 carbon atoms and R 2 is a hydrogen atom.
<4> The lubricant according to <2> or <3> above, wherein R 3 is a hydrocarbon group having 10 to 30 carbon atoms or a hydrocarbon group having 10 to 30 carbon atoms substituted with at least one hydroxy group.
<5> The lubricant according to any one of <1> to <4>, wherein the lubricant A contains at least one of methylolstearic acid amide and methylolbehenic acid amide.
<6> The lubricant according to any one of <1> to <5>, which contains a lubricant B having a melting point lower than that of the lubricant A.
<7> The lubricant according to <6>, wherein the lubricant B has a melting point of 60 ° C. to 80 ° C.
<8> The lubricant B includes oleic acid amide, erucic acid amide, ricinoleic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stealic acid amide, N-stearyl erucate amide, and N. The lubricant according to <6> above, which comprises at least one selected from the group consisting of -oleyl palmitate amide, N-oleyl-hydroxystearic amide, stearic acid, and N-oleyl palmitamide.
<9> The lubricant according to <6>, wherein the lubricant B contains N-oleyl palmitoamide.
<10> The mass ratio of the lubricant A to the lubricant B (lubricant A: lubricant B) is one of the above <6> to <9>, which is 1: 9 to 9: 1. The lubricant described.
<11> The lubricant according to any one of <6> to <10>, wherein the total content of the lubricant A and the lubricant B with respect to the total amount of the lubricant is 50% by mass to 100% by mass. ..
<12> The lubricant according to any one of <1> to <11> used for powder metallurgy.
＜１３＞ 原料粉末と、前記＜１＞～＜１２＞のいずれか１つに記載の潤滑剤と、を含む粉末混合物。
＜１４＞ 前記原料粉末１００質量部に対して、前記潤滑剤の含有量が０．１質量部～２．０質量部である前記＜１３＞に記載の粉末混合物。 <13> A powder mixture containing a raw material powder and the lubricant according to any one of <1> to <12>.
<14> The powder mixture according to <13>, wherein the content of the lubricant is 0.1 parts by mass to 2.0 parts by mass with respect to 100 parts by mass of the raw material powder.
＜１４＞ 前記原料粉末１００質量部に対して、前記潤滑剤の含有量が０．１質量部～２．０質量部である前記＜１３＞に記載の粉末混合物。 <13> A powder mixture containing a raw material powder and the lubricant according to any one of <1> to <12>.
<14> The powder mixture according to <13>, wherein the content of the lubricant is 0.1 parts by mass to 2.0 parts by mass with respect to 100 parts by mass of the raw material powder.
＜１５＞ 前記＜１３＞又は＜１４＞に記載の粉末混合物を焼結することによって焼結体を製造する焼結体の製造方法。
<15> A method for producing a sintered body, which produces a sintered body by sintering the powder mixture according to <13> or <14>.
本開示によれば、粉末混合物の流動性及び圧密性を向上させることができる潤滑剤、これを含む粉末混合物並びに粉末混合物を用いた焼結体の製造方法を提供することができる。
According to the present disclosure, it is possible to provide a lubricant capable of improving the fluidity and compaction property of a powder mixture, a powder mixture containing the same, and a method for producing a sintered body using the powder mixture.
以下、本発明の潤滑剤、粉末混合物及び焼結体の製造方法の実施形態について説明する。但し、本発明は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素（要素ステップ等も含む）は、特に明示した場合を除き、必須ではない。数値及びその範囲についても同様であり、本発明を制限するものではない。
本開示において「～」を用いて示された数値範囲は、「～」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。
本開示中に段階的に記載されている数値範囲において、１つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本開示において各成分は該当する物質を複数種含んでいてもよい。各成分に該当する物質が複数種存在する場合、各成分の含有率又は含有量は、特に断らない限り、当該複数種の物質の合計の含有率又は含有量を意味する。
本開示において各成分に該当する粒子は複数種含んでいてもよい。各成分に該当する粒子が複数種存在する場合、各成分の粒子径は、特に断らない限り、当該複数種の粒子の混合物についての値を意味する。
本開示において、炭化水素基は、飽和炭化水素基であってもよく、不飽和炭化水素基であってもよい。炭化水素基は、直鎖であってもよく、分岐であってもよく、環構造を含むものであってもよい。 Hereinafter, embodiments of the method for producing the lubricant, powder mixture, and sintered body of the present invention will be described. However, the present invention is not limited to the following embodiments. In the following embodiments, the components (including element steps and the like) are not essential unless otherwise specified. The same applies to the numerical values and their ranges, and does not limit the present invention.
The numerical range indicated by using "-" in the present disclosure indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, each component may contain a plurality of applicable substances. When a plurality of substances corresponding to each component are present, the content rate or content of each component means the total content rate or content of the plurality of substances unless otherwise specified.
In the present disclosure, a plurality of types of particles corresponding to each component may be contained. When a plurality of types of particles corresponding to each component are present, the particle size of each component means a value for a mixture of the plurality of types of particles unless otherwise specified.
In the present disclosure, the hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The hydrocarbon group may be linear, branched, or include a ring structure.
本開示において「～」を用いて示された数値範囲は、「～」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。
本開示中に段階的に記載されている数値範囲において、１つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本開示において各成分は該当する物質を複数種含んでいてもよい。各成分に該当する物質が複数種存在する場合、各成分の含有率又は含有量は、特に断らない限り、当該複数種の物質の合計の含有率又は含有量を意味する。
本開示において各成分に該当する粒子は複数種含んでいてもよい。各成分に該当する粒子が複数種存在する場合、各成分の粒子径は、特に断らない限り、当該複数種の粒子の混合物についての値を意味する。
本開示において、炭化水素基は、飽和炭化水素基であってもよく、不飽和炭化水素基であってもよい。炭化水素基は、直鎖であってもよく、分岐であってもよく、環構造を含むものであってもよい。 Hereinafter, embodiments of the method for producing the lubricant, powder mixture, and sintered body of the present invention will be described. However, the present invention is not limited to the following embodiments. In the following embodiments, the components (including element steps and the like) are not essential unless otherwise specified. The same applies to the numerical values and their ranges, and does not limit the present invention.
The numerical range indicated by using "-" in the present disclosure indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, each component may contain a plurality of applicable substances. When a plurality of substances corresponding to each component are present, the content rate or content of each component means the total content rate or content of the plurality of substances unless otherwise specified.
In the present disclosure, a plurality of types of particles corresponding to each component may be contained. When a plurality of types of particles corresponding to each component are present, the particle size of each component means a value for a mixture of the plurality of types of particles unless otherwise specified.
In the present disclosure, the hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The hydrocarbon group may be linear, branched, or include a ring structure.
〔潤滑剤〕
本開示の潤滑剤は、少なくとも１つのヒドロキシ基を有する１価の有機基がアミド結合の窒素原子に少なくとも１つ結合した化合物である潤滑剤Ａを含む。本開示の潤滑剤を粉末混合物の添加剤として用いることにより、粉末混合物の流動性及び圧密性を向上させることができる。この理由は、明らかではないが、極性基であるヒドロキシ基を少なくとも１つ有する１価の有機基がアミド結合の窒素原子に結合していることにより、粉末混合物に添加した際に潤滑剤の極性のバランスが良好であり、粉末混合物の流動性及び圧密性が向上すると考えられる。 〔lubricant〕
The lubricants of the present disclosure include lubricant A, which is a compound in which at least one monovalent organic group having at least one hydroxy group is bonded to an amide-bonded nitrogen atom. By using the lubricant of the present disclosure as an additive of the powder mixture, the fluidity and compaction property of the powder mixture can be improved. The reason for this is not clear, but the polarity of the lubricant when added to the powder mixture due to the fact that a monovalent organic group having at least one hydroxy group, which is a polar group, is bonded to the nitrogen atom of the amide bond. It is considered that the balance between the above is good and the fluidity and compactness of the powder mixture are improved.
本開示の潤滑剤は、少なくとも１つのヒドロキシ基を有する１価の有機基がアミド結合の窒素原子に少なくとも１つ結合した化合物である潤滑剤Ａを含む。本開示の潤滑剤を粉末混合物の添加剤として用いることにより、粉末混合物の流動性及び圧密性を向上させることができる。この理由は、明らかではないが、極性基であるヒドロキシ基を少なくとも１つ有する１価の有機基がアミド結合の窒素原子に結合していることにより、粉末混合物に添加した際に潤滑剤の極性のバランスが良好であり、粉末混合物の流動性及び圧密性が向上すると考えられる。 〔lubricant〕
The lubricants of the present disclosure include lubricant A, which is a compound in which at least one monovalent organic group having at least one hydroxy group is bonded to an amide-bonded nitrogen atom. By using the lubricant of the present disclosure as an additive of the powder mixture, the fluidity and compaction property of the powder mixture can be improved. The reason for this is not clear, but the polarity of the lubricant when added to the powder mixture due to the fact that a monovalent organic group having at least one hydroxy group, which is a polar group, is bonded to the nitrogen atom of the amide bond. It is considered that the balance between the above is good and the fluidity and compactness of the powder mixture are improved.
本開示の潤滑剤は、例えば、粉末冶金用に用いられることが好ましい。また、粉末混合物の潤滑のための、少なくとも１つのヒドロキシ基を有する１価の有機基がアミド結合の窒素原子に少なくとも１つ結合した化合物の使用も本発明の範囲に含まれる。
The lubricant of the present disclosure is preferably used for powder metallurgy, for example. The scope of the present invention also includes the use of compounds in which at least one monovalent organic group having at least one hydroxy group is bonded to the nitrogen atom of the amide bond for lubricating the powder mixture.
（潤滑剤Ａ）
潤滑剤Ａは、少なくとも１つのヒドロキシ基を有する１価の有機基がアミド結合の窒素原子に少なくとも１つ結合した化合物であればよい。潤滑剤Ａは、１種を単独で用いてもよく、２種以上を併用してもよい。 (Lubricant A)
The lubricant A may be a compound in which at least one monovalent organic group having at least one hydroxy group is bonded to the nitrogen atom of the amide bond. As the lubricant A, one type may be used alone, or two or more types may be used in combination.
潤滑剤Ａは、少なくとも１つのヒドロキシ基を有する１価の有機基がアミド結合の窒素原子に少なくとも１つ結合した化合物であればよい。潤滑剤Ａは、１種を単独で用いてもよく、２種以上を併用してもよい。 (Lubricant A)
The lubricant A may be a compound in which at least one monovalent organic group having at least one hydroxy group is bonded to the nitrogen atom of the amide bond. As the lubricant A, one type may be used alone, or two or more types may be used in combination.
また、少なくとも１つのヒドロキシ基を有する１価の有機基としては、炭素数１～３のヒドロキシアルキル基であることが好ましく、メチロール基又はエチロール基であることがより好ましく、メチロール基であることがさらに好ましい。
The monovalent organic group having at least one hydroxy group is preferably a hydroxyalkyl group having 1 to 3 carbon atoms, more preferably a methylol group or an ethylol group, and preferably a methylol group. More preferred.
潤滑剤Ａは、アミド結合のカルボニル基を構成する炭素原子に１価の有機基が結合した化合物であることが好ましい。また、アミド結合のカルボニル基を構成する炭素原子に結合する１価の有機基は、炭素数１０～３０の炭化水素基又は少なくとも１つのヒドロキシ基が置換した炭素数１０～３０の炭化水素基であることが好ましく、炭素数１０～３０の炭化水素基であることがより好ましく、炭素数１５～２５の炭化水素基であることがさらに好ましい。アミド結合のカルボニル基を構成する炭素原子に結合する１価の有機基が、炭素数１０～３０の炭化水素基であることにより、粉末混合物に添加した際に潤滑剤の極性のバランスがより良好であるため、粉末混合物の流動性及び圧密性がより良好となる傾向にある。
Lubricant A is preferably a compound in which a monovalent organic group is bonded to a carbon atom constituting an amide-bonded carbonyl group. The monovalent organic group bonded to the carbon atom constituting the carbonyl group of the amide bond is a hydrocarbon group having 10 to 30 carbon atoms or a hydrocarbon group having 10 to 30 carbon atoms substituted with at least one hydroxy group. It is preferably a hydrocarbon group having 10 to 30 carbon atoms, and further preferably a hydrocarbon group having 15 to 25 carbon atoms. Since the monovalent organic group bonded to the carbon atom constituting the carbonyl group of the amide bond is a hydrocarbon group having 10 to 30 carbon atoms, the polarity balance of the lubricant is better when added to the powder mixture. Therefore, the fluidity and compactness of the powder mixture tend to be better.
潤滑剤Ａは、下記の一般式（１）で表される化合物を含むことが好ましい。
Lubricant A preferably contains a compound represented by the following general formula (1).
一般式（１）中、Ｒ１は少なくとも１つのヒドロキシ基を有する１価の有機基であり、Ｒ２は少なくとも１つのヒドロキシ基を有する１価の有機基又は水素原子であり、Ｒ３は１価の有機基である。
In the general formula (1), R 1 is a monovalent organic group having at least one hydroxy group, R 2 is a monovalent organic group having at least one hydroxy group or a hydrogen atom, and R 3 is 1. It is a valent organic group.
一般式（１）中、Ｒ１及びＲ２における少なくとも１つのヒドロキシ基を有する１価の有機基としては、それぞれ独立に、１つのヒドロキシ基を有する１価の有機基であることが好ましく、炭素数１～３のヒドロキシアルキル基であることがより好ましく、メチロール基又はエチロール基であることがさらに好ましく、メチロール基であることが特に好ましい。
In the general formula (1), the monovalent organic group having at least one hydroxy group in R 1 and R 2 is preferably a monovalent organic group having one hydroxy group independently, preferably carbon. It is more preferably a hydroxyalkyl group of the number 1 to 3, further preferably a methylol group or an ethylol group, and particularly preferably a methylol group.
Ｒ２は水素原子であることが好ましく、Ｒ１は炭素数１～３のヒドロキシアルキル基であり、かつＲ２は水素原子であることがより好ましい。
R 2 is preferably a hydrogen atom, R 1 is a hydroxyalkyl group having 1 to 3 carbon atoms, and R 2 is more preferably a hydrogen atom.
Ｒ３は、炭素数１０～３０の炭化水素基又は少なくとも１つのヒドロキシ基が置換した炭素数１０～３０の炭化水素基であることが好ましく、炭素数１０～３０の炭化水素基であることがより好ましく、炭素数１５～２５の炭化水素基であることがさらに好ましい。
R 3 is preferably a hydrocarbon group having 10 to 30 carbon atoms or a hydrocarbon group having 10 to 30 carbon atoms substituted with at least one hydroxy group, and preferably a hydrocarbon group having 10 to 30 carbon atoms. More preferably, it is a hydrocarbon group having 15 to 25 carbon atoms.
Ｒ３における少なくとも１つのヒドロキシ基が置換した炭素数１０～３０の炭化水素基としては、１つのヒドロキシ基が置換した基であってもよく、２つ以上のヒドロキシ基が置換した基であってもよい。
The at least one hydrocarbon group having 10 to 30 carbon atoms hydroxy group is substituted at the R 3, may be a group in which one hydroxy group is substituted, a group in which two or more hydroxy groups substituted May be good.
潤滑剤Ａとしては、メチロール脂肪酸アミドを含むことが好ましく、アミド結合のカルボニル基を構成する炭素原子に炭素数が１１～２１の炭化水素基が結合したメチロール脂肪酸アミドを含むことがより好ましく、メチロールパルミチン酸アミド、メチロールステアリン酸アミド及びメチロールベヘン酸アミドの少なくともいずれか１つを含むことがさらに好ましく、メチロールステアリン酸アミド及びメチロールベヘン酸アミドの少なくとも一方を含むことが特に好ましく、メチロールステアリン酸アミドを含むことがより一層好ましい。潤滑剤Ａとしては、前述のメチロール脂肪酸アミドであってもよく、前述のメチロール脂肪酸アミドと、メチロール脂肪酸アミド以外の、少なくとも１つのヒドロキシ基を有する１価の有機基がアミド結合の窒素原子に少なくとも１つ結合した化合物との混合物であってもよい。
The lubricant A preferably contains a methylol fatty acid amide, and more preferably contains a methylol fatty acid amide in which a hydrocarbon group having 11 to 21 carbon atoms is bonded to a carbon atom constituting the carbonyl group of the amide bond. It is more preferable to contain at least one of palmitate amide, methylol stearate amide and methylol bechenic acid amide, and particularly preferably to contain at least one of methylol stearate amide and methylol bechenic acid amide. It is even more preferable to include it. The lubricant A may be the above-mentioned methylol fatty acid amide, and at least a monovalent organic group having at least one hydroxy group other than the above-mentioned methylol fatty acid amide and the methylol fatty acid amide is added to the nitrogen atom of the amide bond. It may be a mixture with one bound compound.
潤滑剤Ａの融点は、粉末混合物の流動性を高める点及び成形体の抜出性の点から、９０℃～１４０℃であることが好ましい。
本開示において、融点は示差走査熱量測定（ＤＳＣ）により測定される値である。 The melting point of the lubricant A is preferably 90 ° C. to 140 ° C. from the viewpoint of increasing the fluidity of the powder mixture and the extractability of the molded product.
In the present disclosure, the melting point is a value measured by differential scanning calorimetry (DSC).
本開示において、融点は示差走査熱量測定（ＤＳＣ）により測定される値である。 The melting point of the lubricant A is preferably 90 ° C. to 140 ° C. from the viewpoint of increasing the fluidity of the powder mixture and the extractability of the molded product.
In the present disclosure, the melting point is a value measured by differential scanning calorimetry (DSC).
（潤滑剤Ｂ）
本開示の潤滑剤は、潤滑剤Ａよりも融点が低い潤滑剤Ｂを含むことが好ましい。潤滑剤Ｂを含むことにより、潤滑剤が添加された粉末混合物を金型を用いて圧縮成形した際に、成形体を金型から抜き出しやすくなる、すなわち、成形体の抜き出し性が向上する傾向にある。潤滑剤Ｂは、１種を単独で用いてもよく、２種以上を併用してもよい。 (Lubricant B)
The lubricant of the present disclosure preferably contains a lubricant B having a melting point lower than that of the lubricant A. By containing the lubricant B, when the powder mixture to which the lubricant is added is compression-molded using a mold, the molded product tends to be easily extracted from the mold, that is, the extractability of the molded product tends to be improved. is there. As the lubricant B, one type may be used alone, or two or more types may be used in combination.
本開示の潤滑剤は、潤滑剤Ａよりも融点が低い潤滑剤Ｂを含むことが好ましい。潤滑剤Ｂを含むことにより、潤滑剤が添加された粉末混合物を金型を用いて圧縮成形した際に、成形体を金型から抜き出しやすくなる、すなわち、成形体の抜き出し性が向上する傾向にある。潤滑剤Ｂは、１種を単独で用いてもよく、２種以上を併用してもよい。 (Lubricant B)
The lubricant of the present disclosure preferably contains a lubricant B having a melting point lower than that of the lubricant A. By containing the lubricant B, when the powder mixture to which the lubricant is added is compression-molded using a mold, the molded product tends to be easily extracted from the mold, that is, the extractability of the molded product tends to be improved. is there. As the lubricant B, one type may be used alone, or two or more types may be used in combination.
成形体の抜き出し性の点から、潤滑剤Ｂの融点は６０℃～８０℃であることが好ましい。
From the viewpoint of the extractability of the molded product, the melting point of the lubricant B is preferably 60 ° C to 80 ° C.
潤滑剤Ｂは、オレイン酸アミド、エルカ酸アミド、リシノール酸アミド、Ｎ－オレイルオレイン酸アミド、Ｎ－ステアリルオレイン酸アミド、Ｎ－オレイルステアリン酸アミド、Ｎ－ステアリルエルカ酸アミド、Ｎ－オレイルパルミチン酸アミド、Ｎ－オレイル－ヒドロキシステアリン酸アミド、ステアリン酸、及びＮ－オレイルパルミトアミドからなる群より選択される少なくとも１つを含むことが好ましく、リシノール酸アミド、ステアリン酸、オレイン酸アミド及びＮ－オレイルパルミトアミドからなる群より選択される少なくとも１つを含むことがより好ましい。中でも、粉末混合物の流動性及び圧密性並びに成形体の抜き出し性の点から、Ｎ－オレイルパルミトアミドを含むことがより好ましい。
The lubricant B is oleic acid amide, erucic acid amide, ricinoleic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stealic acid amide, N-stearyl erucic acid amide, N-oleyl palmitic acid. It preferably contains at least one selected from the group consisting of amides, N-oleyl-hydroxystearic amides, stearic acids, and N-oleyl palmitoamides, preferably ricinolic acid amides, stearic acids, oleic acid amides and N-. More preferably, it comprises at least one selected from the group consisting of oleyl palmitoamide. Above all, it is more preferable to contain N-oleyl palmitoamide from the viewpoint of fluidity and compaction of the powder mixture and extractability of the molded product.
潤滑剤Ａと潤滑剤Ｂとの質量比（潤滑剤Ａ：潤滑剤Ｂ）は、粉末混合物の流動性及び圧密性並びに成形体の抜き出し性のバランスの点から、１：９～９：１であることが好ましく、２：８～８：２であることがより好ましく、３：７～７：３であることがさらに好ましい。
The mass ratio of the lubricant A to the lubricant B (lubricant A: lubricant B) is 1: 9 to 9: 1 from the viewpoint of the balance between the fluidity and compaction of the powder mixture and the extractability of the molded product. It is preferably 2: 8 to 8: 2, and even more preferably 3: 7 to 7: 3.
潤滑剤全量に対する潤滑剤Ａ及び潤滑剤Ｂの合計の含有率は、５０質量％～１００質量％であることが好ましい。また、潤滑剤Ａ及び潤滑剤Ｂの合計の含有率は、６０質量％～９５質量％であってもよく、８０質量％～９０質量％であってもよい。
The total content of the lubricant A and the lubricant B with respect to the total amount of the lubricant is preferably 50% by mass to 100% by mass. Further, the total content of the lubricant A and the lubricant B may be 60% by mass to 95% by mass, or 80% by mass to 90% by mass.
本開示の潤滑剤としては、潤滑剤Ａはメチロール脂肪酸アミドであり、潤滑剤ＢはＮ－オレイルパルミトアミドであることが好ましい。これにより、粉末混合物の流動性及び圧密性並びに成形体の抜き出し性のバランスに優れる傾向にある。
As the lubricant of the present disclosure, it is preferable that the lubricant A is a methylol fatty acid amide and the lubricant B is N-oleyl palmitoamide. As a result, the balance between the fluidity and compaction of the powder mixture and the extractability of the molded product tends to be excellent.
（その他の潤滑剤）
本開示の潤滑剤は、潤滑剤Ａ及び潤滑剤Ｂ以外のその他の潤滑剤を含んでいてもよい。その他の潤滑剤としては、潤滑剤Ａ及び潤滑剤Ｂ以外のアミド系潤滑剤が挙げられる。その他の潤滑剤は、１種を単独で用いてもよく、２種以上を併用してもよい。 (Other lubricants)
The lubricant of the present disclosure may contain a lubricant other than the lubricant A and the lubricant B. Examples of other lubricants include amide-based lubricants other than lubricant A and lubricant B. As for other lubricants, one type may be used alone, or two or more types may be used in combination.
本開示の潤滑剤は、潤滑剤Ａ及び潤滑剤Ｂ以外のその他の潤滑剤を含んでいてもよい。その他の潤滑剤としては、潤滑剤Ａ及び潤滑剤Ｂ以外のアミド系潤滑剤が挙げられる。その他の潤滑剤は、１種を単独で用いてもよく、２種以上を併用してもよい。 (Other lubricants)
The lubricant of the present disclosure may contain a lubricant other than the lubricant A and the lubricant B. Examples of other lubricants include amide-based lubricants other than lubricant A and lubricant B. As for other lubricants, one type may be used alone, or two or more types may be used in combination.
潤滑剤Ａ及び潤滑剤Ｂ以外のアミド系潤滑剤としては、潤滑剤Ｂよりも融点の高い、脂肪酸アミド、脂肪酸ビスアミド等が挙げられる。
Examples of the amide-based lubricant other than the lubricant A and the lubricant B include fatty acid amide and fatty acid bisamide, which have a higher melting point than the lubricant B.
脂肪酸アミドとしては、ラウリン酸アミド、パルチミン酸アミド、ステアリン酸アミド、ベヘン酸アミド、ヒドロキシステアリン酸アミド、Ｎ－ラウリルラウリン酸アミド、Ｎ－パルミチルパルミチン酸アミド、Ｎ－ステアリルステアリン酸アミド、Ｎ－ステアリル－ヒドロキシステアリン酸アミド等が挙げられる。
Examples of the fatty acid amide include lauric acid amide, partiminic acid amide, stearic acid amide, bechenic acid amide, hydroxystearic acid amide, N-lauryl lauric acid amide, N-palmityl palmitate amide, N-stearyl stealic acid amide, and N-. Examples thereof include stearyl-hydroxystearic acid amide.
また、脂肪酸ビスアミドとしては、メチレンビスステアリン酸アミド、メチレンビスラウリン酸アミド、メチレンビスヒドロキシステアリン酸アミド、エチレンビスカプリル酸アミド、エチレンビスカプリン酸アミド、エチレンビスラウリン酸アミド、エチレンビスステアリン酸アミド、エチレンビスイソステアリン酸アミド、エチレンビスヒドロキシステアリン酸アミド、エチレンビスベヘン酸アミド、ヘキサメチレンビスステアリン酸アミド、ヘキサメチレンビスベヘン酸アミド、ヘキサメチレンビスヒドロキシステアリン酸アミド、ブチレンビスヒドロキシステアリン酸アミド、Ｎ，Ｎ’－ジステアリルアジピン酸アミド、Ｎ，Ｎ’－ジステアリルセバシン酸アミド、メチレンビスオレイン酸アミド、エチレンビスオレイン酸アミド、エチレンビスエルカ酸アミド、ヘキサメチレンビスオレイン酸アミド、Ｎ，Ｎ’－ジオレイルアジピン酸アミド、Ｎ，Ｎ’－ジオレイルセバシン酸アミド、ｍ－キシリレンビスステアリン酸アミド、Ｎ，Ｎ’－ジステアリルイソフタル酸アミド等が挙げられる。
Examples of the fatty acid bisamide include methylene bisstearic acid amide, methylene bislauric acid amide, methylene bishydroxystearic acid amide, ethylene biscaprylic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, and ethylene bisstearic acid amide. Ethylenebisisostearic acid amide, ethylenebishydroxystearic acid amide, ethylenebisbechenic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisbechenic acid amide, hexamethylene bishydroxystearic acid amide, butylene bishydroxystearic acid amide, N, N'-distearyl adipate amide, N, N'-distearyl sebacic acid amide, methylenebisoleic acid amide, ethylenebisoleic acid amide, ethylenebiserucic acid amide, hexamethylenebisoleic acid amide, N, N'- Examples thereof include dioleyl adipate amide, N, N'-diorail sebacic acid amide, m-xylylene bisstearic acid amide, N, N'-distearyl isophthalic acid amide and the like.
潤滑剤全量に対するその他の潤滑剤の含有率は、０質量％超５０質量％以下であってもよく、５質量％～４０質量％であってもよく、１０質量％～２０質量％であってもよい。
The content of the other lubricant with respect to the total amount of the lubricant may be more than 0% by mass and 50% by mass or less, 5% by mass to 40% by mass, or 10% by mass to 20% by mass. May be good.
〔粉末混合物〕
本開示の粉末混合物は、原料粉末と、前述の本開示の潤滑剤と、を含む。この粉末混合物は、流動性及び圧密性に優れる。
本開示の粉末混合物は、例えば、粉末冶金用に用いられることが好ましい。 [Powder mixture]
The powder mixture of the present disclosure includes a raw material powder and the above-mentioned lubricant of the present disclosure. This powder mixture is excellent in fluidity and consolidation.
The powder mixture of the present disclosure is preferably used, for example, for powder metallurgy.
本開示の粉末混合物は、原料粉末と、前述の本開示の潤滑剤と、を含む。この粉末混合物は、流動性及び圧密性に優れる。
本開示の粉末混合物は、例えば、粉末冶金用に用いられることが好ましい。 [Powder mixture]
The powder mixture of the present disclosure includes a raw material powder and the above-mentioned lubricant of the present disclosure. This powder mixture is excellent in fluidity and consolidation.
The powder mixture of the present disclosure is preferably used, for example, for powder metallurgy.
原料粉末としては、鉄を主成分として含む主原料粉末、焼結体の特性を改善する副原料粉末等が挙げられる。
なお、鉄を主成分として含むとは、原料粉末における鉄の含有率が原料粉末全体の５０質量％以上であることを意味する。 Examples of the raw material powder include a main raw material powder containing iron as a main component, an auxiliary raw material powder for improving the characteristics of the sintered body, and the like.
The fact that iron is contained as a main component means that the iron content in the raw material powder is 50% by mass or more of the total raw material powder.
なお、鉄を主成分として含むとは、原料粉末における鉄の含有率が原料粉末全体の５０質量％以上であることを意味する。 Examples of the raw material powder include a main raw material powder containing iron as a main component, an auxiliary raw material powder for improving the characteristics of the sintered body, and the like.
The fact that iron is contained as a main component means that the iron content in the raw material powder is 50% by mass or more of the total raw material powder.
主原料粉末としては、不可避不純物（酸素、ケイ素、炭素、マンガン等）を含みうる純鉄粉、鉄基合金粉末等の鉄基粉末が挙げられる。主原料粉末は、１種を単独で用いてもよく、２種以上を併用してもよい。
Examples of the main raw material powder include pure iron powder that can contain unavoidable impurities (oxygen, silicon, carbon, manganese, etc.) and iron-based powder such as iron-based alloy powder. As the main raw material powder, one type may be used alone, or two or more types may be used in combination.
主原料粉末の平均粒子径は、３０μｍ～１５０μｍであることが好ましく、５０μｍ～１００μｍであることがより好ましい。
本開示において、平均粒子径は、レーザー回折法により測定される体積基準の粒度分布において小径側からの累積が５０％となるときの粒子径（Ｄ５０）である。 The average particle size of the main raw material powder is preferably 30 μm to 150 μm, more preferably 50 μm to 100 μm.
In the present disclosure, the average particle size is the particle size (D50) when the cumulative amount from the small diameter side is 50% in the volume-based particle size distribution measured by the laser diffraction method.
本開示において、平均粒子径は、レーザー回折法により測定される体積基準の粒度分布において小径側からの累積が５０％となるときの粒子径（Ｄ５０）である。 The average particle size of the main raw material powder is preferably 30 μm to 150 μm, more preferably 50 μm to 100 μm.
In the present disclosure, the average particle size is the particle size (D50) when the cumulative amount from the small diameter side is 50% in the volume-based particle size distribution measured by the laser diffraction method.
鉄基粉末は、例えば、アトマイズ法によって溶融鉄又は溶融鉄合金を微粒子とした後に還元し、次いで粉砕する方法によって製造できる。
The iron-based powder can be produced, for example, by a method in which molten iron or a molten iron alloy is made into fine particles by an atomizing method, reduced, and then pulverized.
副原料粉末としては、焼結体の特性を改善することができる原料粉末であれば特に限定されず、焼結体の硬さ、靭性等の機械的特性を向上させる粉末、焼結体の被削性を高める粉末等が挙げられる。
The auxiliary raw material powder is not particularly limited as long as it is a raw material powder that can improve the characteristics of the sintered body, and is a powder that improves mechanical properties such as hardness and toughness of the sintered body, and a cover of the sintered body. Examples include powders that enhance shaving properties.
副原料粉末としては、例えば、主原料粉末以外の金属粉末及び無機粉末が挙げられる。副原料粉末は、１種を単独で用いてもよく、２種以上を併用してもよい。
Examples of the auxiliary raw material powder include metal powders and inorganic powders other than the main raw material powder. As the auxiliary raw material powder, one type may be used alone, or two or more types may be used in combination.
金属粉末としては、銅、ニッケル、クロム、モリブデン、スズ、バナジウム、マンガン等の粉末が挙げられる。
Examples of the metal powder include powders of copper, nickel, chromium, molybdenum, tin, vanadium, manganese and the like.
無機粉末としては、硫化マンガン、二硫化マンガン等の硫化物；窒化ホウ素等の窒化物；ホウ酸、酸化マグネシウム、酸化カリウム、酸化ケイ素等の酸化物；天然黒鉛、人造黒鉛等のグラファイト；リン；硫黄などの粉末が挙げられる。
Examples of the inorganic powder include sulfides such as manganese sulfide and manganese disulfide; nitrides such as boron nitride; oxides such as boric acid, magnesium oxide, potassium oxide and silicon oxide; graphite such as natural graphite and artificial graphite; phosphorus; Examples include powders such as sulfur.
副原料粉末の平均粒子径は、２μｍ～１００μｍであることが好ましく、５μｍ～５０μｍであることがより好ましい。
The average particle size of the auxiliary raw material powder is preferably 2 μm to 100 μm, and more preferably 5 μm to 50 μm.
原料粉末１００質量部のうち、主原料粉末の含有量は、９０質量部～９９質量部であることが好ましく、９５質量部～９８質量部であることがより好ましい。
Of 100 parts by mass of the raw material powder, the content of the main raw material powder is preferably 90 parts by mass to 99 parts by mass, and more preferably 95 parts by mass to 98 parts by mass.
原料粉末１００質量部のうち、副原料粉末の含有量は、１質量部～１０質量部であることが好ましく、２質量部～５質量部であることがより好ましい。
Of 100 parts by mass of the raw material powder, the content of the auxiliary raw material powder is preferably 1 part by mass to 10 parts by mass, and more preferably 2 parts by mass to 5 parts by mass.
原料粉末１００質量部に対して、潤滑剤の含有量は、０．１質量部～２．０質量部であることが好ましく、０．２質量部～１．５質量部であることがより好ましく、０．３質量部～１．０質量部であることがさらに好ましい。
The content of the lubricant is preferably 0.1 part by mass to 2.0 part by mass, and more preferably 0.2 part by mass to 1.5 part by mass with respect to 100 parts by mass of the raw material powder. , 0.3 parts by mass to 1.0 part by mass is more preferable.
（その他の成分）
本開示の粉末混合物は、原料粉末及び本開示の潤滑剤以外のその他の成分を含んでいてもよい。その他の成分としては、バインダーが挙げられる。粉末混合物がバインダーを含むことにより、原料粉末の偏析、飛散等を抑制できる傾向にある。 (Other ingredients)
The powder mixture of the present disclosure may contain a raw material powder and other components other than the lubricant of the present disclosure. Other components include binders. Since the powder mixture contains a binder, segregation, scattering, etc. of the raw material powder tend to be suppressed.
本開示の粉末混合物は、原料粉末及び本開示の潤滑剤以外のその他の成分を含んでいてもよい。その他の成分としては、バインダーが挙げられる。粉末混合物がバインダーを含むことにより、原料粉末の偏析、飛散等を抑制できる傾向にある。 (Other ingredients)
The powder mixture of the present disclosure may contain a raw material powder and other components other than the lubricant of the present disclosure. Other components include binders. Since the powder mixture contains a binder, segregation, scattering, etc. of the raw material powder tend to be suppressed.
バインダーとしては、特に限定されず、ポリオレフィン、アクリル樹脂、ポリスチレン、スチレンブタジエンゴム、エチレングリコールジステアレート、エポキシ樹脂、ロジンエステル等が挙げられる。
The binder is not particularly limited, and examples thereof include polyolefin, acrylic resin, polystyrene, styrene-butadiene rubber, ethylene glycol distearate, epoxy resin, rosin ester, and the like.
本開示の粉末混合物がバインダーを含む場合、バインダーの含有量は、原料粉末１００質量部に対して、０．０１質量部～１．０質量部であることが好ましく、０．１質量部～１．０質量部であることがより好ましい。
When the powder mixture of the present disclosure contains a binder, the content of the binder is preferably 0.01 part by mass to 1.0 part by mass, and 0.1 part by mass to 1 part by mass with respect to 100 parts by mass of the raw material powder. More preferably, it is 0.0 parts by mass.
本開示の粉末混合物は、原料粉末と、本開示の潤滑剤と、必要に応じてその他の成分とを混合することにより得られる。原料粉末と、本開示の潤滑剤との混合は、羽根付き混合機、Ｖ形混合機、二重円錐形混合機（Ｗコーン）等の通常使用されている混合機を用いて行うことができる。
The powder mixture of the present disclosure is obtained by mixing the raw material powder, the lubricant of the present disclosure, and other components as needed. The raw material powder and the lubricant of the present disclosure can be mixed by using a commonly used mixer such as a bladed mixer, a V-shaped mixer, or a bicone mixer (W cone). ..
〔焼結体の製造方法〕
本開示の焼結体の製造方法は、本開示の粉末混合物を焼結することによって焼結体を製造する方法である。
本開示の焼結体の製造方法は、好ましくは、本開示の粉末混合物を金型内に充填すること、金型内に充填された粉末混合物を圧縮成形して成形体とすること、及び、金型内から抜き出した成形体を焼結することを含んでいる。 [Manufacturing method of sintered body]
The method for producing a sintered body of the present disclosure is a method of producing a sintered body by sintering the powder mixture of the present disclosure.
The method for producing a sintered body of the present disclosure preferably comprises filling a mold with the powder mixture of the present disclosure, compression molding the powder mixture filled in the mold to obtain a molded product, and the like. It includes sintering the molded product extracted from the mold.
本開示の焼結体の製造方法は、本開示の粉末混合物を焼結することによって焼結体を製造する方法である。
本開示の焼結体の製造方法は、好ましくは、本開示の粉末混合物を金型内に充填すること、金型内に充填された粉末混合物を圧縮成形して成形体とすること、及び、金型内から抜き出した成形体を焼結することを含んでいる。 [Manufacturing method of sintered body]
The method for producing a sintered body of the present disclosure is a method of producing a sintered body by sintering the powder mixture of the present disclosure.
The method for producing a sintered body of the present disclosure preferably comprises filling a mold with the powder mixture of the present disclosure, compression molding the powder mixture filled in the mold to obtain a molded product, and the like. It includes sintering the molded product extracted from the mold.
本開示の焼結体の製造方法では、本開示の粉末混合物が流動性に優れるため、本開示の粉末混合物は金型内への充填性に優れ、効率よく焼結体を製造でき、さらに、本開示の粉末混合物は圧密性に優れるため、圧縮成形により得られる成形体の密度を高めることができ、強度等の機械的特性に優れる焼結体を製造できる。
また、本開示の焼結体の製造方法では、本開示の粉末混合物が潤滑剤Ｂを含む場合に粉末混合物の成形体を金型内から抜き出すときの圧力を低減することができる。 In the method for producing a sintered body of the present disclosure, since the powder mixture of the present disclosure is excellent in fluidity, the powder mixture of the present disclosure is excellent in filling property into a mold, and a sintered body can be efficiently produced. Since the powder mixture of the present disclosure is excellent in compactness, the density of the molded product obtained by compression molding can be increased, and a sintered body having excellent mechanical properties such as strength can be produced.
Further, in the method for producing a sintered body of the present disclosure, when the powder mixture of the present disclosure contains a lubricant B, the pressure when the molded product of the powder mixture is taken out from the mold can be reduced.
また、本開示の焼結体の製造方法では、本開示の粉末混合物が潤滑剤Ｂを含む場合に粉末混合物の成形体を金型内から抜き出すときの圧力を低減することができる。 In the method for producing a sintered body of the present disclosure, since the powder mixture of the present disclosure is excellent in fluidity, the powder mixture of the present disclosure is excellent in filling property into a mold, and a sintered body can be efficiently produced. Since the powder mixture of the present disclosure is excellent in compactness, the density of the molded product obtained by compression molding can be increased, and a sintered body having excellent mechanical properties such as strength can be produced.
Further, in the method for producing a sintered body of the present disclosure, when the powder mixture of the present disclosure contains a lubricant B, the pressure when the molded product of the powder mixture is taken out from the mold can be reduced.
本開示の焼結体の製造方法では、金型内に充填された粉末混合物を圧縮成形してもよい。成形温度、成形圧力等は特に限定されず、粉末混合物の組成、添加量、金型内の形状等によって適宜調節してもよい。
In the method for producing a sintered body of the present disclosure, the powder mixture filled in the mold may be compression molded. The molding temperature, molding pressure and the like are not particularly limited, and may be appropriately adjusted depending on the composition of the powder mixture, the amount of addition, the shape in the mold and the like.
本開示の焼結体の製造方法では、粉末混合物を焼結することによって焼結体を製造し、好ましくは金型内から抜き出した成形体を焼結することによって焼結体を製造する。粉末混合物又は成形体を焼結する条件としては、特に限定されず、通常の焼結方法を採用することができる。
In the method for producing a sintered body of the present disclosure, a sintered body is manufactured by sintering a powder mixture, and preferably a sintered body is manufactured by sintering a molded body extracted from a mold. The conditions for sintering the powder mixture or the molded product are not particularly limited, and a normal sintering method can be adopted.
以下、実施例に基づき本開示をさらに詳細に説明する。なお、本発明は以下の実施例によって限定されるものではない。
Hereinafter, the present disclosure will be described in more detail based on the examples. The present invention is not limited to the following examples.
［実施例１～４０及び比較例１～６０］
主原料粉末として、平均粒子径が７５μｍの粉末冶金用アトマイズ鉄粉、副原料粉末として平均粒子径が３０μｍの電解銅粉、及び平均粒子径が１０μｍの黒鉛粉を用意した。次に、鉄粉９７．５質量部、銅粉１．５質量部及び黒鉛粉１．０質量部に対し、表１～表５及び以下に示す潤滑剤Ａ又はその他の潤滑剤、及び潤滑剤Ｂの潤滑剤混合物を０．８質量部加えた。各実施例及び各比較例にて加えた潤滑剤Ａ又はその他の潤滑剤及び潤滑剤Ｂの割合は表１～表５に示すとおりである。その後、これらの混合物をＶ形混合機に投入し、３０分混合することで各実施例及び各比較例の粉末混合物を得た。
＜潤滑剤Ａ＞
メチロールステアリン酸アミド（融点：１１０℃）
メチロールベヘン酸アミド（融点：１１３℃）
＜潤滑剤Ｂ＞
Ｎ－オレイルパルミトアミド（融点：７０℃）
リシノール酸アミド（融点：６２℃）
ステアリン酸（融点：６９℃）
オレイン酸アミド（融点：７５℃）
＜その他の潤滑剤＞
ヒドロキシステアリン酸アミド（融点：１０７℃）
エチレンビスステアリン酸アミド（融点：１４５℃）
ステアリン酸アミド（融点：１０１℃） [Examples 1 to 40 and Comparative Examples 1 to 60]
As the main raw material powder, atomized iron powder for powder metallurgy having an average particle size of 75 μm, electrolytic copper powder having an average particle size of 30 μm, and graphite powder having an average particle size of 10 μm were prepared as auxiliary raw material powders. Next, with respect to 97.5 parts by mass of iron powder, 1.5 parts by mass of copper powder, and 1.0 part by mass of graphite powder, lubricant A or other lubricants shown in Tables 1 to 5 and the following, and lubricants. 0.8 parts by mass of the lubricant mixture of B was added. The ratios of the lubricant A or other lubricants and the lubricant B added in each Example and each Comparative Example are as shown in Tables 1 to 5. Then, these mixtures were put into a V-type mixer and mixed for 30 minutes to obtain a powder mixture of each Example and each Comparative Example.
<Lubricant A>
Methylolpropane amide (melting point: 110 ° C)
Methylolpropane amide (melting point: 113 ° C)
<Lubricant B>
N-oleyl palmitoamide (melting point: 70 ° C)
Ricinoleic acid amide (melting point: 62 ° C)
Stearic acid (melting point: 69 ° C)
Oleic acid amide (melting point: 75 ° C)
<Other lubricants>
Hydroxystearic acid amide (melting point: 107 ° C)
Ethylene bisstearic acid amide (melting point: 145 ° C)
Stearic acid amide (melting point: 101 ° C)
主原料粉末として、平均粒子径が７５μｍの粉末冶金用アトマイズ鉄粉、副原料粉末として平均粒子径が３０μｍの電解銅粉、及び平均粒子径が１０μｍの黒鉛粉を用意した。次に、鉄粉９７．５質量部、銅粉１．５質量部及び黒鉛粉１．０質量部に対し、表１～表５及び以下に示す潤滑剤Ａ又はその他の潤滑剤、及び潤滑剤Ｂの潤滑剤混合物を０．８質量部加えた。各実施例及び各比較例にて加えた潤滑剤Ａ又はその他の潤滑剤及び潤滑剤Ｂの割合は表１～表５に示すとおりである。その後、これらの混合物をＶ形混合機に投入し、３０分混合することで各実施例及び各比較例の粉末混合物を得た。
＜潤滑剤Ａ＞
メチロールステアリン酸アミド（融点：１１０℃）
メチロールベヘン酸アミド（融点：１１３℃）
＜潤滑剤Ｂ＞
Ｎ－オレイルパルミトアミド（融点：７０℃）
リシノール酸アミド（融点：６２℃）
ステアリン酸（融点：６９℃）
オレイン酸アミド（融点：７５℃）
＜その他の潤滑剤＞
ヒドロキシステアリン酸アミド（融点：１０７℃）
エチレンビスステアリン酸アミド（融点：１４５℃）
ステアリン酸アミド（融点：１０１℃） [Examples 1 to 40 and Comparative Examples 1 to 60]
As the main raw material powder, atomized iron powder for powder metallurgy having an average particle size of 75 μm, electrolytic copper powder having an average particle size of 30 μm, and graphite powder having an average particle size of 10 μm were prepared as auxiliary raw material powders. Next, with respect to 97.5 parts by mass of iron powder, 1.5 parts by mass of copper powder, and 1.0 part by mass of graphite powder, lubricant A or other lubricants shown in Tables 1 to 5 and the following, and lubricants. 0.8 parts by mass of the lubricant mixture of B was added. The ratios of the lubricant A or other lubricants and the lubricant B added in each Example and each Comparative Example are as shown in Tables 1 to 5. Then, these mixtures were put into a V-type mixer and mixed for 30 minutes to obtain a powder mixture of each Example and each Comparative Example.
<Lubricant A>
Methylolpropane amide (melting point: 110 ° C)
Methylolpropane amide (melting point: 113 ° C)
<Lubricant B>
N-oleyl palmitoamide (melting point: 70 ° C)
Ricinoleic acid amide (melting point: 62 ° C)
Stearic acid (melting point: 69 ° C)
Oleic acid amide (melting point: 75 ° C)
<Other lubricants>
Hydroxystearic acid amide (melting point: 107 ° C)
Ethylene bisstearic acid amide (melting point: 145 ° C)
Stearic acid amide (melting point: 101 ° C)
（粉末混合物の流動性）
各実施例及び各比較例で得た粉末混合物の流動性の評価は、ＪＩＳ Ｚ ２５０２（２０１２）に規定された流動度試験方法により行った。評価基準は以下の通りである。
－評価基準－
Ａ 粉末混合物が３０秒以内に流れた。
Ｂ 粉末混合物が３０秒超３５秒以内に流れた。
Ｃ 粉末混合物が流れない、又は粉末混合物が３５秒超で流れた。
結果を表１～表５に示す。評価Ａ又は評価Ｂであれば、粉末混合物の流動性は良好である。 (Fluidity of powder mixture)
The fluidity of the powder mixture obtained in each Example and each Comparative Example was evaluated by the fluidity test method specified in JIS Z 2502 (2012). The evaluation criteria are as follows.
-Evaluation criteria-
A powder mixture flowed within 30 seconds.
B The powder mixture flowed over 30 seconds and within 35 seconds.
C The powder mixture did not flow, or the powder mixture flowed in more than 35 seconds.
The results are shown in Tables 1-5. If it is evaluation A or evaluation B, the fluidity of the powder mixture is good.
各実施例及び各比較例で得た粉末混合物の流動性の評価は、ＪＩＳ Ｚ ２５０２（２０１２）に規定された流動度試験方法により行った。評価基準は以下の通りである。
－評価基準－
Ａ 粉末混合物が３０秒以内に流れた。
Ｂ 粉末混合物が３０秒超３５秒以内に流れた。
Ｃ 粉末混合物が流れない、又は粉末混合物が３５秒超で流れた。
結果を表１～表５に示す。評価Ａ又は評価Ｂであれば、粉末混合物の流動性は良好である。 (Fluidity of powder mixture)
The fluidity of the powder mixture obtained in each Example and each Comparative Example was evaluated by the fluidity test method specified in JIS Z 2502 (2012). The evaluation criteria are as follows.
-Evaluation criteria-
A powder mixture flowed within 30 seconds.
B The powder mixture flowed over 30 seconds and within 35 seconds.
C The powder mixture did not flow, or the powder mixture flowed in more than 35 seconds.
The results are shown in Tables 1-5. If it is evaluation A or evaluation B, the fluidity of the powder mixture is good.
（粉末混合物の圧密性）
各実施例及び各比較例で得た粉末混合物の圧密性の評価は、粉末混合物７ｇを金型内に供給した後に、成形圧力７００ＭＰａで直径１１．３ｍｍの円柱成形体を成形し、以下の基準に基づき行った。
－評価基準－
Ａ 円柱成形体の密度が７．１０ｇ／ｃｍ３以上であった。
Ｂ 円柱成形体の密度が７．０６ｇ／ｃｍ３以上７．１０ｇ／ｃｍ３未満であった。
Ｃ 円柱成形体の密度が７．０６ｇ／ｃｍ３未満であった。
結果を表１～表５に示す。評価Ａ又は評価Ｂであれば、粉末混合物の圧密性は良好である。 (Consolidation of powder mixture)
In the evaluation of the compactness of the powder mixture obtained in each Example and each Comparative Example, after supplying 7 g of the powder mixture into the mold, a cylindrical molded body having a diameter of 11.3 mm was molded at a molding pressure of 700 MPa, and the following criteria were used. It was done based on.
-Evaluation criteria-
A The density of the cylindrical molded body was 7.10 g / cm 3 or more.
The density of the B columnar molded product was 7.06 g / cm 3 or more and less than 7.10 g / cm 3 .
The density of the C-cylindrical compact was less than 7.06 g / cm 3 .
The results are shown in Tables 1-5. If it is evaluation A or evaluation B, the compaction property of the powder mixture is good.
各実施例及び各比較例で得た粉末混合物の圧密性の評価は、粉末混合物７ｇを金型内に供給した後に、成形圧力７００ＭＰａで直径１１．３ｍｍの円柱成形体を成形し、以下の基準に基づき行った。
－評価基準－
Ａ 円柱成形体の密度が７．１０ｇ／ｃｍ３以上であった。
Ｂ 円柱成形体の密度が７．０６ｇ／ｃｍ３以上７．１０ｇ／ｃｍ３未満であった。
Ｃ 円柱成形体の密度が７．０６ｇ／ｃｍ３未満であった。
結果を表１～表５に示す。評価Ａ又は評価Ｂであれば、粉末混合物の圧密性は良好である。 (Consolidation of powder mixture)
In the evaluation of the compactness of the powder mixture obtained in each Example and each Comparative Example, after supplying 7 g of the powder mixture into the mold, a cylindrical molded body having a diameter of 11.3 mm was molded at a molding pressure of 700 MPa, and the following criteria were used. It was done based on.
-Evaluation criteria-
A The density of the cylindrical molded body was 7.10 g / cm 3 or more.
The density of the B columnar molded product was 7.06 g / cm 3 or more and less than 7.10 g / cm 3 .
The density of the C-cylindrical compact was less than 7.06 g / cm 3 .
The results are shown in Tables 1-5. If it is evaluation A or evaluation B, the compaction property of the powder mixture is good.
（円柱成形体の抜き出し性）
各実施例及び各比較例における円柱成形体の抜き出し性は、前述の粉末混合物の圧密性の評価に用いる円柱成形体を金型から抜き出す際に抜出圧力の測定を行い、以下の基準に基づいて評価した。
－評価基準－
Ａ 抜出圧力は８ＭＰａ以下であった。
Ｂ 抜出圧力は８ＭＰａ超１５ＭＰａ以下であった。
Ｃ 抜出圧力は１５ＭＰａ超であった。
結果を表１～表５に示す。評価Ａ又は評価Ｂであれば、円柱成形体の抜き出し性は良好である。 (Pullability of cylindrical molded body)
The extractability of the cylindrical molded product in each of the examples and the comparative examples is based on the following criteria by measuring the extraction pressure when the cylindrical molded product used for evaluating the compaction property of the powder mixture described above is extracted from the mold. Evaluated.
-Evaluation criteria-
A Extraction pressure was 8 MPa or less.
B The extraction pressure was more than 8 MPa and less than 15 MPa.
The C extraction pressure was more than 15 MPa.
The results are shown in Tables 1-5. If the evaluation is A or B, the extraction property of the cylindrical molded product is good.
各実施例及び各比較例における円柱成形体の抜き出し性は、前述の粉末混合物の圧密性の評価に用いる円柱成形体を金型から抜き出す際に抜出圧力の測定を行い、以下の基準に基づいて評価した。
－評価基準－
Ａ 抜出圧力は８ＭＰａ以下であった。
Ｂ 抜出圧力は８ＭＰａ超１５ＭＰａ以下であった。
Ｃ 抜出圧力は１５ＭＰａ超であった。
結果を表１～表５に示す。評価Ａ又は評価Ｂであれば、円柱成形体の抜き出し性は良好である。 (Pullability of cylindrical molded body)
The extractability of the cylindrical molded product in each of the examples and the comparative examples is based on the following criteria by measuring the extraction pressure when the cylindrical molded product used for evaluating the compaction property of the powder mixture described above is extracted from the mold. Evaluated.
-Evaluation criteria-
A Extraction pressure was 8 MPa or less.
B The extraction pressure was more than 8 MPa and less than 15 MPa.
The C extraction pressure was more than 15 MPa.
The results are shown in Tables 1-5. If the evaluation is A or B, the extraction property of the cylindrical molded product is good.
表１～表５に示すように、実施例１～４０の粉末混合物は、比較例１～６０の粉末混合物と比較して流動性及び圧密性に優れていた。
さらに、実施例１～４０の粉末混合物は、抜き出し性についても良好であった。 As shown in Tables 1 to 5, the powder mixture of Examples 1 to 40 was superior in fluidity and compaction as compared with the powder mixture of Comparative Examples 1 to 60.
Further, the powder mixture of Examples 1 to 40 was also good in extractability.
さらに、実施例１～４０の粉末混合物は、抜き出し性についても良好であった。 As shown in Tables 1 to 5, the powder mixture of Examples 1 to 40 was superior in fluidity and compaction as compared with the powder mixture of Comparative Examples 1 to 60.
Further, the powder mixture of Examples 1 to 40 was also good in extractability.
本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.
Claims (15)
- 少なくとも１つのヒドロキシ基を有する１価の有機基がアミド結合の窒素原子に少なくとも１つ結合した化合物である潤滑剤Ａを含む潤滑剤。 A lubricant containing a lubricant A, which is a compound in which at least one monovalent organic group having at least one hydroxy group is bonded to an amide-bonded nitrogen atom.
- 前記潤滑剤Ａは、下記の一般式（１）で表される化合物を含む請求項１に記載の潤滑剤。
（一般式（１）中、Ｒ１は少なくとも１つのヒドロキシ基を有する１価の有機基であり、Ｒ２は少なくとも１つのヒドロキシ基を有する１価の有機基又は水素原子であり、Ｒ３は１価の有機基である。） The lubricant according to claim 1, wherein the lubricant A contains a compound represented by the following general formula (1).
(In the general formula (1), R 1 is a monovalent organic group having at least one hydroxy group, R 2 is a monovalent organic group having at least one hydroxy group or a hydrogen atom, and R 3 is. It is a monovalent organic group.) - Ｒ１は炭素数１～３のヒドロキシアルキル基であり、Ｒ２は水素原子である請求項２に記載の潤滑剤。 The lubricant according to claim 2, wherein R 1 is a hydroxyalkyl group having 1 to 3 carbon atoms and R 2 is a hydrogen atom.
- Ｒ３は、炭素数１０～３０の炭化水素基又は少なくとも１つのヒドロキシ基が置換した炭素数１０～３０の炭化水素基である請求項２又は請求項３に記載の潤滑剤。 The lubricant according to claim 2 or 3 , wherein R 3 is a hydrocarbon group having 10 to 30 carbon atoms or a hydrocarbon group having 10 to 30 carbon atoms substituted with at least one hydroxy group.
- 前記潤滑剤Ａは、メチロールステアリン酸アミド及びメチロールベヘン酸アミドの少なくとも一方を含む請求項１～請求項４のいずれか１項に記載の潤滑剤。 The lubricant according to any one of claims 1 to 4, wherein the lubricant A contains at least one of methylolstearic acid amide and methylolbehenic acid amide.
- 前記潤滑剤Ａよりも融点が低い潤滑剤Ｂを含む請求項１～請求項５のいずれか１項に記載の潤滑剤。 The lubricant according to any one of claims 1 to 5, which contains a lubricant B having a melting point lower than that of the lubricant A.
- 前記潤滑剤Ｂの融点が６０℃～８０℃である請求項６に記載の潤滑剤。 The lubricant according to claim 6, wherein the lubricant B has a melting point of 60 ° C to 80 ° C.
- 前記潤滑剤Ｂは、オレイン酸アミド、エルカ酸アミド、リシノール酸アミド、Ｎ－オレイルオレイン酸アミド、Ｎ－ステアリルオレイン酸アミド、Ｎ－オレイルステアリン酸アミド、Ｎ－ステアリルエルカ酸アミド、Ｎ－オレイルパルミチン酸アミド、Ｎ－オレイル－ヒドロキシステアリン酸アミド、ステアリン酸、及びＮ－オレイルパルミトアミドからなる群より選択される少なくとも１つを含む請求項６に記載の潤滑剤。 The lubricant B is oleic acid amide, erucic acid amide, ricinoleic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stealic acid amide, N-stearyl erucate amide, N-oleyl palmitin. The lubricant according to claim 6, which comprises at least one selected from the group consisting of acid amides, N-oleyl-hydroxystearic acid amides, stearic acids, and N-oleyl palmitoamides.
- 前記潤滑剤Ｂは、Ｎ－オレイルパルミトアミドを含む請求項６に記載の潤滑剤。 The lubricant according to claim 6, wherein the lubricant B contains N-oleyl palmitoamide.
- 前記潤滑剤Ａと前記潤滑剤Ｂとの質量比（潤滑剤Ａ：潤滑剤Ｂ）は、１：９～９：１である請求項６～請求項９のいずれか１項に記載の潤滑剤。 The lubricant according to any one of claims 6 to 9, wherein the mass ratio of the lubricant A to the lubricant B (lubricant A: lubricant B) is 1: 9 to 9: 1. ..
- 潤滑剤全量に対する前記潤滑剤Ａ及び前記潤滑剤Ｂの合計の含有率は、５０質量％～１００質量％である請求項６～請求項１０のいずれか１項に記載の潤滑剤。 The lubricant according to any one of claims 6 to 10, wherein the total content of the lubricant A and the lubricant B with respect to the total amount of the lubricant is 50% by mass to 100% by mass.
- 粉末冶金に用いる請求項１～請求項１１のいずれか１項に記載の潤滑剤。 The lubricant according to any one of claims 1 to 11, which is used for powder metallurgy.
- 原料粉末と、請求項１～請求項１２のいずれか１項に記載の潤滑剤と、を含む粉末混合物。 A powder mixture containing a raw material powder and the lubricant according to any one of claims 1 to 12.
- 前記原料粉末１００質量部に対して、前記潤滑剤の含有量が０．１質量部～２．０質量部である請求項１３に記載の粉末混合物。 The powder mixture according to claim 13, wherein the content of the lubricant is 0.1 parts by mass to 2.0 parts by mass with respect to 100 parts by mass of the raw material powder.
- 請求項１３又は請求項１４に記載の粉末混合物を焼結することによって焼結体を製造する焼結体の製造方法。 A method for producing a sintered body, which produces a sintered body by sintering the powder mixture according to claim 13 or 14.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2019/013415 WO2020194616A1 (en) | 2019-03-27 | 2019-03-27 | Lubricant, powdered mixture, and method for producing sintered body |
| JP2021509391A JPWO2020196401A1 (en) | 2019-03-27 | 2020-03-23 | |
| PCT/JP2020/012708 WO2020196401A1 (en) | 2019-03-27 | 2020-03-23 | Lubricant, powdered mixture, and method for producing sintered body |
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| PCT/JP2019/013415 WO2020194616A1 (en) | 2019-03-27 | 2019-03-27 | Lubricant, powdered mixture, and method for producing sintered body |
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| PCT/JP2020/012708 WO2020196401A1 (en) | 2019-03-27 | 2020-03-23 | Lubricant, powdered mixture, and method for producing sintered body |
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| CN114589301A (en) * | 2022-02-21 | 2022-06-07 | 湖南航天磁电有限责任公司 | Lubricant for powder molding and integrally molded inductance powder containing same |
| EP4105301A1 (en) * | 2021-06-15 | 2022-12-21 | Basf Se | New gasoline additive packages |
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| JPWO2020196401A1 (en) | 2020-10-01 |
| WO2020196401A1 (en) | 2020-10-01 |
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