JP6436128B2 - Mixed powder for powder metallurgy - Google Patents

Description

  The present invention relates to a mixed powder for powder metallurgy.

  Powder metallurgy is a technique for producing a sintered part such as a machine part by pressing a mixed powder containing an iron-based powder and the like to obtain a green compact and then sintering the green compact. In recent years, the progress of powder metallurgy technology has made it possible to manufacture sintered parts having a complicated shape with high dimensional accuracy in a near net shape, and therefore, powder metallurgy technology is used for manufacturing products in various fields.

  However, if sintered parts require extremely strict dimensional accuracy, or if a side hole shape, undercut shape, or other highly complex shape is required, post-sintering ( Cutting etc.) may be required.

  However, sintered parts are high in strength for post-processing and have a high pore content ratio, so that the cutting resistance and frictional heat are large, and the surface temperature of the cutting tool tends to increase. Therefore, there is a problem that the cutting tool is easily worn out and has a short life, resulting in an increase in cutting cost and an increase in manufacturing cost of the sintered part.

  Therefore, as a solution to the above problem, so-called green processing, in which sintering is performed after the green compact before being sintered, is attracting attention. However, generally, the green compact before sintering is brittle and the workability is often insufficient. That is, the green compact before sintering cannot withstand the stress applied to the jig during green processing or during cutting, and is easily damaged. For this reason, it is desired to increase the strength of the green compact so that it can withstand green processing.

  As a technique for increasing the strength of a green compact, for example, in Patent Document 1, in a metal powder composition containing an iron-based powder and a lubricant powder, the lubricant powder has a weight average molecular weight MW of 2,000. It has been proposed to use an amide type oligomer having a melting point peak in the range of ˜20,000 and a melting point peak of 120˜200 ° C. According to Patent Document 1, the green powder strength is improved by preheating the metal powder composition to a temperature 5 to 50 ° C. lower than the melting point of the amide oligomer and performing warm molding.

  Patent Document 2 proposes to use a combination of substance A, substance B, and substance C as the lubricant in a metal powder composition containing iron-based powder and lubricant powder. Here, substance A is a polyolefin, substance B is a substance selected from the group consisting of saturated and unsaturated fatty acid (bis) amides, saturated fatty acid alcohols, and fatty acid glycerol, and substance C has a molecular weight of 500 to 30,000 g / mol. It is an amide oligomer having According to Patent Document 2, by using a lubricant combined with the substances A to C, not only powder properties such as apparent density and fluidity are strengthened, but also high green strength is obtained by heat treating the green compact. Is supposed to be obtained.

  In Patent Document 3, polyethylene ether having an average molecular weight in the range of 50,000 to 400,000 g / mol, the remaining weight average molecular weight in the range of 2,000 to 20,000 g / mol, and a melting point peak in the range of 120 ° C to 200 ° C. Lubricants for powder metallurgy compositions comprising oligomeric amides having the following have been proposed. According to Patent Document 3, it is described that by using the lubricant, it is possible to improve the green compact strength and to have durability when being extracted from the molding die.

  Furthermore, Patent Document 4 proposes a mixed powder for powder metallurgy containing a thermosetting resin powder. As the thermosetting resin, one or more selected from the group consisting of an epoxy / polyester resin, an epoxy resin, and an acrylic resin is used. According to Patent Document 4, a green compact obtained using the powder mixture for powder metallurgy as a raw material has an appropriate density and strength even before sintering, and can be machined.

Japanese Patent No. 3803371 Special table 2013-503976 gazette Japanese Patent No. 4300110 JP 2006-124777 A

  However, although the mixed powder for powder metallurgy proposed in Patent Document 1 is supposed to improve the green compact strength by performing warm forming, in general molding performed at room temperature, the powder compact is so high. The body strength could not be obtained.

  Similarly, the powder powder metallurgy mixed powder proposed in Patent Document 2 cannot obtain a high green compact strength by general molding performed at room temperature, and it is removed from the mold after compacting. There was a problem that the output was high when it was put out.

  Further, Patent Document 3 only discloses the use of oligomeric amide, and does not describe the use of a polymer having a higher number of monomer bonds. Further, there is no description of using a low melting point polymer (resin) having a melting point lower than 120 ° C.

  On the other hand, although the use of a thermosetting resin is proposed in Patent Document 4, if the resin powder is simply added to the mixed powder for powder metallurgy, it is discharged from the hopper during transportation due to the difference in mass from the iron-based powder. There is a concern that segregation is likely to occur at the time of transfer, such as mold filling, and the like, resulting in product quality variations. In addition, resin powders are more likely to generate dust than iron-based powders, and there are concerns about human health risks due to large amounts of suction or continuous inhalation, and it is considered that countermeasures are required in the work itself and the workplace environment.

  As a method of suppressing such segregation and dust generation, premixing is performed by heating and mixing at a predetermined temperature at the time of manufacturing the mixed powder, and attaching a compound having a small mass to the iron-based powder surface via a binder. Can be considered. However, when premixing was performed on the powder metallurgy mixed powder described in Patent Document 3, it was found that the effect of improving the green compact strength was not sufficiently exhibited depending on the conditions.

  Moreover, in mixed powders for powder metallurgy, for example, fluidity at the time of transfer such as discharging from a storage hopper or filling into a mold is one of the important characteristics affecting production speed and filling properties. . Therefore, in order to realize improvement in product quality and reduction in manufacturing cost, it is required that the mixed powder for powder metallurgy has good fluidity. However, when the present inventors examined the mixed powder for powder metallurgy described in Patent Document 4, it was found that fluidity may be insufficient.

  The present invention has been made in view of the above points, and has good fluidity at the time of powder transfer and pullability at the time of compacting, and processing before sintering when compacted. An object of the present invention is to provide a powder mixture for powder metallurgy, which can obtain a high-quality product (sintered body) and further reduce health risks.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by the following constitution, and have completed the present invention. That is, the gist configuration of the present invention is as follows.

1. A powder mixture for powder metallurgy comprising an iron-based powder, a copolymerized polyamide having a melting point of 80 to 120 ° C., a first microcapsule, and a second microcapsule,
The first microcapsule includes a first liquid curable compound,
The second microcapsule includes at least one of a second liquid curable compound different from the first liquid curable compound, a curing agent, and a curing accelerator;
The mixed powder for powder metallurgy, wherein the content of the liquid curable compound not encapsulated in the microcapsules in the mixed powder for powder metallurgy is 0.10 parts by mass or less with respect to 100 parts by mass of the iron-based powder.

2. 2. The mixed powder for powder metallurgy according to 1 above, wherein the content of the copolymerized polyamide is 0.05 to 0.4 parts by mass with respect to 100 parts by mass of the iron-based powder.

3. The powder metallurgy mixing according to 1 or 2, wherein a total content of the first microcapsules and the second microcapsules is 0.05 to 2 parts by mass with respect to 100 parts by mass of the iron-based powder. Powder.

4). The mixed powder for powder metallurgy according to any one of claims 1 to 3, wherein the iron-based powder is coated with the copolymerized polyamide.

  ADVANTAGE OF THE INVENTION According to this invention, the fluidity | liquidity at the time of powder transfer and the extraction property at the time of compacting are favorable, and when making it a compact, it can provide the mixed powder for powder metallurgy having high strength. Moreover, by using the mixed powder for powder metallurgy as a premix powder, it is possible to provide a mixed powder for powder metallurgy with improved product quality and reduced health risks.

  Hereinafter, the mixed powder for powder metallurgy according to the present invention will be specifically described.

[Mixed powder for powder metallurgy]
The mixed powder for powder metallurgy (hereinafter also simply referred to as “mixed powder”) of the present invention contains an iron-based powder, a copolymerized polyamide having a melting point of 80 to 120 ° C., a first microcapsule, and a second microcapsule. It is a mixed powder for powder metallurgy. The first microcapsule includes a first liquid curable compound, and the second microcapsule is a second liquid curable compound different from the first liquid curable compound, It contains at least one of a curing agent and a curing accelerator. Furthermore, the content of the liquid curable compound not encapsulated in the microcapsule in the powder mixture for powder metallurgy is 0.10 parts by mass or less with respect to 100 parts by mass of the iron-based powder.

  The mixed powder of the present invention has good pullability during compacting and high strength when formed into a compact. Further, the fluidity is good, and the workability before sintering is excellent when a green compact is formed. The reason why the mixed powder of the present invention has such excellent characteristics is presumed as follows.

  First, since the mixed powder of the present invention contains a copolymerized polyamide, the adhesion of the iron-based powder particles is reinforced by the adhesive strength of the copolymerized polyamide. Furthermore, since the mixed powder of the present invention contains microcapsules enclosing a liquid curable compound, the liquid curable compound oozes out from the microcapsules during molding and spreads between the particles of the iron-based powder. The particles are bonded together. As a result, the green compact obtained by pressure molding the mixed powder of the present invention has high strength even before sintering, and can perform processing such as cutting while suppressing damage ( It is considered that the processability is excellent.

  Further, in the mixed powder of the present invention, the liquid curable compound is encapsulated in the microcapsule, and the content of the liquid curable compound not encapsulated in the microcapsule is 0. The amount is 10 parts by mass or less. Thus, since the content of the liquid curable compound not encapsulated in the microcapsule is so low that it can be said that it is not substantially contained, the particles of the iron-based powder are in a liquid state before pressure molding. It is thought that it is excellent in fluidity without being adhered by the curable compound. On the other hand, mixed powder for powder metallurgy containing a curable resin powder (see, for example, Patent Document 4) is considered to have relatively good workability before sintering when formed into a green compact. However, it is considered that the fluidity is inferior because adhesion performance can be exhibited even before pressure molding.

  Next, each component contained in the mixed powder of the present invention will be described.

[Iron-based powder]
Any iron-based powder can be used without any particular limitation. Here, “iron-based powder” means a powder having an Fe content of 50% by mass or more. Examples of the iron-based powder include pure iron powder and alloy steel powder.

  As said pure iron powder, arbitrary things, such as atomized iron powder (atomized iron powder), reduced iron powder (reduced iron powder), can be used, for example. Examples of the alloy steel powder include partially diffused alloyed steel powder obtained by partially diffusing the alloy component into iron powder, fully alloyed steel powder containing the alloy component from the time of melting, and fully alloyed steel powder. Furthermore, arbitrary things, such as hybrid steel powder in which the alloy component was partially diffused, can be used. Examples of the alloy component in the alloy steel powder include Cr, Mn, Ni, Mo, V, Cu, and Nb. In particular, Ni, Mo, Cu, and the like can be added by diffusion bonding. The content of the alloy component in the iron-based powder is not particularly limited, and can be any value as long as the premise of being an iron-based powder (Fe: 50% by mass or more) is satisfied.

  It is allowed that impurities other than Fe and alloy components are contained in the iron-based powder. In addition, it is preferable that the total content of the impurities in the iron-based powder is 3% by mass or less. Typical impurities contained in the iron-based powder include C, Si, Mn, P, S, O, N and the like. When these impurities are contained in the iron-based powder, the respective contents are mass%, C: 0.05% or less, Si: 0.10% or less, Mn (when not added as an alloy element): 0 50% or less, P: 0.03% or less, S: 0.03% or less, O: 0.50% or less, and N: 0.1% or less are preferable.

  The average particle diameter of the iron-based powder is not particularly limited and may be any value, but it is preferably 70 to 100 μm as a normal range used for powder metallurgy. Here, unless otherwise specified, the average particle size of the iron-based powder is a value measured by dry sieving in accordance with JIS Z 2510: 2004.

[Copolymer polyamide]
The copolymerized polyamide is not particularly limited, and any copolymerized polyamide can be used. From the viewpoint of adhesion to iron-based powder, the melting point of the copolymerized polyamide is 80 to 120 ° C. If the melting point of the copolymerized polyamide is 80 to 120 ° C., when the iron-based powder or copolymerized polyamide is heated and mixed in order to produce the mixed powder, the copolymerized polyamide is favorably applied to the surface of the iron-based powder. Can be attached.

  Examples of the monomer constituting the copolymer polyamide include (A) lactam or aminocarboxylic acid constituting polycaproamide, polydodecanamide, etc .; (B) polytetramethylene adipamide, polypentamethylene adipamide, Examples thereof include salts in which an equimolar amount of dicarboxylic acid and diamine constituting polypentamethylene sebacamide, polyhexamethylene adipamide, polyhexamethylene sebacamide, polyhexamethylene dodecanamide and the like are combined. For example, a copolymer obtained by copolymerizing any two or more monomers selected from (A) and (B) can be used as the copolymerized polyamide. Examples of the monomer include (i) ε-caprolactam constituting polycaproamide; (ii) hexamethylenediammonium adipate (AH salt) constituting polyhexamethylene adipamide; (iii) polyhexamethylene sebacamide. Containing hexamethylene diammonium sebacate (SH salt); (iv) A quaternary copolymer comprising ω-laurolactam constituting polydodecanamide, and comprising the monomers (i) to (iv) above More preferably.

[[Average particle diameter of copolymerized polyamide]]
The average particle diameter of the copolymerized polyamide is not particularly limited and can be set to any value. However, if the average particle size is too large, the density of the mixed powder may decrease and the desired strength may be difficult to obtain, and if it is too small, the fluidity may be insufficient. The average particle size is preferably 5 to 100 μm. When the average particle size of the copolymerized polyamide is within the above range, the fluidity of the mixed powder becomes better, and the workability before sintering when it is made into a green compact is more excellent. Here, the “average particle diameter” of the copolymerized polyamide refers to the volume average particle diameter, and can be measured using a laser diffraction / scattering particle size distribution meter.

[[Copolymer polyamide content]]
The content of the copolymerized polyamide in the mixed powder of the present invention is not particularly limited and can be any value. However, if the content of the copolymerized polyamide is too small, sufficient strength may be difficult to obtain. If the content is too large, the density of the green compact may decrease, so copolymerization in the powder mixture for powder metallurgy The content of the polyamide is preferably 0.05 to 0.4 parts by mass, more preferably 0.1 to 0.2 parts by mass with respect to 100 parts by mass of the iron-based powder.

[Microcapsule]
The mixed powder for powder metallurgy of the present invention contains a first microcapsule and a second microcapsule. A microcapsule is one in which an encapsulant (core substance) is encapsulated inside a capsule wall made of a membrane substance, and the first microcapsule and the second microcapsule in the present invention are different as described below. Contains an internal packaging.

  The first microcapsule contains a first liquid curable compound. In contrast, the second microcapsule includes at least one of a second liquid curable compound, a curing agent, and a curing accelerator different from the first liquid curable compound. Thus, in the mixed powder of the present invention, since the liquid curable compound exists in a microencapsulated state, the particles of the iron-based powder are not adhered to each other in a state before pressure molding, Excellent fluidity. In this specification, “liquid” means liquid at normal temperature (25 ° C.). Similarly, “powdered” means solid at room temperature. In addition, the first microcapsule and the second microcapsule can further include components other than those described above.

  First, items common to the first microcapsule and the second microcapsule will be described. In the following description, the first microcapsule and the second microcapsule may be collectively referred to as “microcapsule”. Similarly, the first liquid curable compound and the second liquid curable compound may be collectively referred to as “liquid curable compound”.

  The method for encapsulating the encapsulating agent such as a liquid curable compound is not particularly limited, and any method such as a conventionally known method can be used. Examples include, but are not limited to, a Solid in Oil (S / O) microcapsule method, a phase separation method, an interfacial polymerization method, an in-situ polymerization method, and a spray drying method. The manufacturing method of the first microcapsule and the manufacturing method of the second microcapsule may be the same or different, and are selected independently according to the capsule wall material to be used and the material of the encapsulating agent. be able to.

  The material of the capsule wall of the microcapsule (capsule wall material) is not particularly limited, and any material such as a resin can be used. Examples include urea resins, melamine-formaldehyde resins, polyester resins, styrene acrylic resins, and the like, but are not limited to these resins. The wall material of the first microcapsule and the wall material of the second microcapsule may be the same or different.

  In the microcapsule, the mass ratio of the encapsulating agent to the capsule wall (encapsulating agent / capsule wall) is not particularly limited, but may be, for example, 99/1 to 50/50, and 95/5 to 70/30. It is preferable to do. The mass ratio between the encapsulating agent and the capsule wall may be the same or different between the first microcapsule and the second microcapsule, and can be set independently.

[[Average particle size of microcapsules]]
The average particle diameters of the first microcapsules and the second microcapsules are not particularly limited, and can be arbitrarily set to arbitrary values. However, if the average particle size is too large, the density of the mixed powder may be reduced, making it difficult to obtain the desired strength. If the average particle size is too small, the fluidity may be insufficient. Therefore, the average particle size of the microcapsules is preferably 5 to 100 μm. When the average particle size of the microcapsules is within the above range, the fluidity of the mixed powder becomes better, and the workability before sintering when it is made into a green compact is more excellent. The average particle size of the microcapsules is more preferably 20 to 90 μm, and further preferably 30 to 80 μm. Here, the “average particle diameter” of the microcapsules refers to a volume average particle diameter, which can be measured using a laser diffraction / scattering particle size distribution meter.

[[Microcapsule content]]
The content of the first microcapsule and the second microcapsule in the powder mixture for powder metallurgy (hereinafter sometimes simply referred to as “content of microcapsule”) is not particularly limited, It can be any value. However, if the content of the microcapsules is too small, the encapsulating agent does not sufficiently bleed out during pressure molding, and it may be difficult to obtain sufficient strength. Conversely, if the content of the microcapsules is too large, the inclusion agent oozes out of the green compact and adheres to the mold, and the extractability deteriorates, and the necking between the iron-based powder particles is inhibited. The strength may decrease. Therefore, the total content of the first microcapsules and the second microcapsules is preferably 0.05 to 2 parts by mass, and 0.08 to 1.5 parts by mass with respect to 100 parts by mass of the iron-based powder. It is more preferable to set it as 0.10-1.0 mass part.

  The mixed powder for powder metallurgy is usually often mixed with a lubricant (release agent) in order to improve the pullability after pressure molding. However, in the mixed powder of the present invention, microcapsules are used. Since the extractability can be improved by containing the mixed powder, it is allowed that the mixed powder does not contain a lubricant. However, blending a lubricant with the mixed powder of the present invention is not excluded.

[Internal packaging]
As described above, the first and second microcapsules contain a liquid curable compound (hereinafter also simply referred to as “curable compound”), a curing agent, a curing accelerator, and the like as an inclusion agent. The internal packaging agent exudes from the microcapsule when the powder mixture of the present invention is pressure-molded to obtain a green compact, and bonds the iron-based powder particles together.

  The first liquid curable compound and the second liquid curable compound are not particularly limited, and any liquid curable compound can be used. For example, a curable compound used as an adhesive can be used, and specifically includes urethane, epoxy, (meth) acrylic, modified silicone (epoxy / modified silicone, acryl / modified silicone), etc. Liquid curable compounds such as, but not limited to. Here, “(meth) acrylate” means “acrylate and / or methacrylate”.

  In addition, the curing agent and the curing accelerator that are the encapsulating agent of the second microcapsule are not particularly limited, and any curing agent and curing accelerator such as those used for the adhesive can be used.

  Next, examples of the encapsulating agent of the first microcapsule and the second microcapsule will be described. In the following examples, for the sake of convenience, the curing agent of the first liquid curable compound is expressed as “first curing agent”, and the curing accelerator of the first liquid curable compound is expressed as “first curing accelerator”. To do. Similarly, the curing agent of the second liquid curable compound is referred to as “second curing agent”, and the curing accelerator of the second liquid curable compound is referred to as “second curing accelerator”.

  The first microcapsules only have to contain at least the first liquid curable compound. Therefore, the encapsulating agent of the first microcapsules may be only the first liquid curable compound, At least one of the curing agent and the first curing accelerator can be included together with the first liquid curable compound. Further, when the encapsulating agent of the second microcapsule contains the second liquid curable compound, at least one of the second curing agent and the second curing accelerator is further encapsulated in the first microcapsule. It can also be made.

Therefore, the encapsulating agent of the first microcapsule is, for example,
(1) a first liquid curable compound,
(2) a first liquid curable compound and a first curing agent,
(3) a first liquid curable compound and a second curing agent,
(4) 1st liquid curable compound, 1st hardening | curing agent, and 2nd hardening | curing agent, or (5) 1st liquid curable compound, 1st hardening accelerator, and 2nd hardening accelerator ,
It can be.

On the other hand, the second microcapsules may include at least one of a second liquid curable compound, a curing agent, and a curing accelerator different from the first liquid curable compound. Here, as the curing agent, for example, a first curing agent can be used, but when the second microcapsule encapsulates the second liquid curable compound, the second curing agent is further encapsulated. You can also. Similarly, as the curing accelerator, for example, a first curing accelerator can be used. However, when the second microcapsule encapsulates the second liquid curable compound, the second curing accelerator is further used. Can also be included.
As the curing accelerator, the first curing agent and the first curing accelerator can be used.

Therefore, the inclusion agent of the second microcapsule is, for example,
(1) a second liquid curable compound,
(2) a second liquid curable compound, a first curing accelerator, and a second curing accelerator,
(3) a first curing agent,
(4) a first curing agent and a first curing accelerator,
(5) the first curing accelerator, or (6) the first liquid curable compound and the first curing accelerator,
It can be. The first curing agent and the second curing agent may be the same, and the first curing accelerator and the second curing accelerator may be the same.

  When using a urethane-based liquid curable compound, for example, a polyol as a first liquid curable compound is encapsulated in a first microcapsule, and a urethane prepolymer or a curing agent as a second liquid curable compound is used. The polyisocyanate can be encapsulated in the second microcapsule. At this time, the amount of the curing agent to be encapsulated in the second microcapsule is determined based on the first liquid curable compound encapsulated in the first microcapsule and the second liquid curable compound encapsulated in the second microcapsule. The total amount is preferably about 3 to 20 parts by mass with respect to 100 parts by mass.

  When using an epoxy-based liquid curable compound, for example, an epoxy resin prepolymer is encapsulated as a first liquid curable compound in a first microcapsule, and a fatty acid polyamine as a curing agent and a tertiary as a curing accelerator. The amine can be encapsulated in the second microcapsule. At this time, the mass ratio (epoxy resin prepolymer: curing agent: curing accelerator) of these encapsulating agents is preferably 50 to 90: 5 to 40: 0.1 to 20. The mass ratio of the microcapsules (first microcapsule / second microcapsule) is preferably 50/50 to 99.9 / 0.1.

  When a (meth) acrylic liquid curable compound is used, for example, (meth) acrylic monomer as the first liquid curable compound and an organic peroxide as the curing agent are encapsulated in the first microcapsule to accelerate curing. A tertiary amine as an agent can be encapsulated in the second second microcapsule. At this time, the content of the first microcapsule in the encapsulating agent is preferably (meth) acrylic monomer: 90 to 99.9% by mass, and organic peroxide: 0.1 to 10% by mass. The mass ratio of the microcapsules (first first microcapsule / second microcapsule) is preferably 90/10 to 99.9 / 0.1.

  As another form, for example, a (meth) acrylic monomer as the first liquid curable compound and an organic peroxide as the curing agent are encapsulated in the first microcapsule, and the second liquid curable compound is used. The (meth) acrylic monomer and the soluble vanadium compound as a reducing agent for the (meth) acrylic monomer can be encapsulated in the second microcapsule. The (meth) acrylic monomer as the first liquid curable compound and the (meth) acrylic monomer as the second liquid curable compound may be the same. At this time, the content of the first microcapsule in the encapsulating agent is preferably (meth) acrylic monomer: 90 to 99.9% by mass, and organic peroxide: 0.1 to 10% by mass. The content of the second microcapsule in the encapsulating agent is preferably (meth) acrylic monomer: 90 to 99.95% by mass, soluble vanadium compound: 0.05 to 10% by mass. Furthermore, the mass ratio of the microcapsules (first microcapsule / second microcapsule) is preferably 50/50 to 99.9 / 0.1.

  As another form, for example, the (meth) acrylic monomer as the first liquid curable compound and the organic peroxide as the curing agent are encapsulated in the first microcapsule, and the second liquid curable compound is used. The (meth) acrylic monomer and a tertiary amine as a curing accelerator can be encapsulated in the second microcapsule. The (meth) acrylic monomer as the first liquid curable compound and the (meth) acrylic monomer as the second liquid curable compound may be the same. At this time, the content of the first microcapsule in the encapsulating agent is preferably (meth) acrylic monomer: 90 to 99.9% by mass, and organic peroxide: 0.1 to 10% by mass. The content of the second microcapsule in the encapsulating agent is preferably (meth) acrylic monomer: 90 to 99.9% by mass and tertiary amine: 0.1 to 10% by mass. Furthermore, the mass ratio of the microcapsules (first microcapsule / second microcapsule) is preferably 50/50 to 99.9 / 0.1.

  Here, examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and dodecyl (meth). Alkyl (meth) acrylates such as acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; glycidyl Glycidyl (meth) acrylates such as (meth) acrylate and glycidylalkyl (meth) acrylate; alkoxyalkyl (meth) acrylates; allyl (meth) acrylate, allylalkyl (meta Allylic alkyl (meth) acrylates such as acrylates; polyfunctional (meth) acrylates such as monoethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate; For example, but not limited to.

  Examples of the tertiary amine include heterocyclic tertiary amines such as quinoline, methylquinoline, quinaldine, quinoxaline, and phenazine; N, N-dimethyl-anisidine, N, N-dimethylaniline, N, N-dimethyl- aromatic tertiary amines such as p-toluidine; and the like, but are not limited thereto.

  Examples of the organic peroxide include hydrones such as cumene hydroperoxide, t-butyl hydroperoxide, p-methane hydroperoxide, methyl ethyl ketone peroxide, cyclohexane peroxide, dicumyl peroxide, and diisopropylbenzene hydroperoxide. Examples include, but are not limited to, peroxides; ketone peroxides; diallyl peroxides; peroxyesters;

  When the modified silicone resin-based liquid curable compound is used, for example, the modified silicone resin as the first liquid curable compound and the fatty acid polyamine as the curing agent are encapsulated in the first microcapsule, and the second liquid curable property is obtained. The epoxy resin as the compound and the organic tin as the curing accelerator can be encapsulated in the second microcapsule. At this time, the content of the first microcapsule in the encapsulating agent is preferably modified silicone resin: 90 to 99% by mass and fatty acid polyamine: 1 to 10% by mass. The content of the second microcapsule in the encapsulant is preferably epoxy resin: 90 to 99.9% by mass, and organic tin: 0.1 to 10% by mass. Furthermore, the mass ratio of the microcapsules (first microcapsule / second microcapsule) is preferably 50/50 to 99.9 / 0.1.

  The molecular weight (including the weight average molecular weight and the number average molecular weight) of the first and second liquid curable compounds is not particularly limited as long as it is liquid, and is appropriately set.

[Liquid curable compound not encapsulated in microcapsules]
In the present invention, the content of the liquid curable compound not encapsulated in the microcapsules in the powder mixture for powder metallurgy is set to 0.10 parts by mass or less with respect to 100 parts by mass of the iron-based powder. Thereby, in the state before press-molding the mixed powder of this invention, the particle | grains of iron-based powder are not adhere | attached, but it is excellent in fluidity | liquidity. As the liquid curable compound that is not encapsulated in the microcapsule, for example, those described as the liquid curable compound that is the encapsulating agent of the microcapsule can be used. The content of the liquid curable compound not encapsulated in the microcapsule is more preferably 0.01 parts by mass or less with respect to 100 parts by mass of the iron-based powder, and the liquid curable compound not encapsulated in the microcapsule More preferably, it does not contain substantially. Here, “substantially does not contain a liquid curable compound not encapsulated in microcapsules” means that “a liquid curable compound not encapsulated in microcapsules is not added to the powder mixture for powder metallurgy”. means.

[Other additives]
The mixed powder of the present invention can optionally contain other additives in addition to the above-described components, if necessary, in a state where they are not encapsulated in microcapsules. As said other additive, at least 1 sort (s) selected from the group which consists of a hardening | curing agent, a hardening accelerator, a plasticizer, and a coupling agent can be used, for example. The other additives may be liquid or powdery. Further, a lubricant can be contained as an additive. As the lubricant, for example, at least one selected from the group consisting of metal soap (such as zinc stearate), fatty acid amide, amide wax, copolymerized polyamide, polyethylene, and oxidized polyethylene can be used.

[Production method and usage of mixed powder for powder metallurgy]
Next, a method for producing and using a mixed powder for powder metallurgy according to the present invention will be described. The following description relates to one embodiment of the present invention, and the present invention is not limited to this.

  The mixed powder of the present invention can be obtained by appropriately mixing the above-described essential components and optional components using, for example, a mixer. For example, a copolymerized polyamide, and optionally an alloy powder are added to the iron-based powder, and the mixture is primarily mixed. During the primary mixing, the surface of the iron-based powder can be covered with the copolymerized polyamide by stirring while heating to the melting point of the copolymerized polyamide or higher and gradually cooling while mixing. In addition, when alloy powder and other additives are added. These components also adhere to the surface of the iron-based powder.

 There is no restriction | limiting in particular as a means to perform the said mixing, Various mixers can be used. As the mixer, for example, a V-type mixer, a high-speed bottom-stirring mixer that can be easily heated, an inclined rotary pan-type mixer, a rotary mulberry type mixer, a conical planetary screw type mixer, and the like are particularly preferably used. .

  The mixed powder of the present invention thus obtained can be used as a raw material for powder metallurgy. That is, the mixed powder of the present invention is pressure-molded by an arbitrary method to form a green compact (a green compact), and then the green compact is sintered at 1000 to 1300 ° C., for example. Sintered parts such as can be manufactured. At this time, the mixed powder of the present invention is excellent in fluidity at the time of transfer such as discharging from a storage hopper or filling into a mold when being pressure-molded. Expected to improve quality and reduce manufacturing costs. Further, the green compact obtained by pressure-molding the mixed powder of the present invention is increased in strength while maintaining the density, and cutting, etc. while suppressing damage even before sintering. Can be processed (green processing).

[Curing treatment]
When a thermosetting compound such as acrylic, phenolic, and epoxy type is used as the liquid curable compound, after the green compact molding, a curing treatment for further curing the liquid curable compound ( Heat treatment) can also be performed. The strength of the green compact can be further improved by curing the liquid curable compound by heating. The conditions for the curing treatment may be determined according to the type of the thermosetting liquid compound to be used, but are generally in the range of 80 to 200 ° C. for 10 minutes to 1 hour, more preferably in the range of 15 to 30 minutes. It is preferable to carry out with.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to the following examples at all.

<Example 1>
An iron-based powder prepared by adding copper powder: 2% by mass and graphite powder: 0.8% by mass to pure iron powder (atomized iron powder 301A manufactured by JFE Steel) was prepared. 0.2 parts by mass (primary addition) of copolymerized polyamide particles (melting point 116 ° C., average particle size 40 μm) was added, and the mixture was heated and mixed at a temperature of 150 ° C. using a high-speed bottom stirring mixer. Subsequently, after slow cooling, the microcapsule 1 encapsulating the (meth) acrylic monomer as the first liquid curable compound and the organic peroxide as the curing agent, and the (meta) as the second liquid curable compound ) Add 0.25 parts by mass (secondary addition) of microcapsules 2 containing acrylic monomer and tertiary amine as a curing accelerator to 100 parts by mass of iron-based powder, and add V-type blender. And mixed at room temperature for 15 minutes to obtain a mixed powder for powder metallurgy. The mixed powder for powder metallurgy is not added with a liquid curable compound that is not encapsulated in microcapsules. Therefore, the mixed powder for powder metallurgy substantially contains a liquid curable compound that is not encapsulated in microcapsules. Not contained. In addition, as the microcapsule 1 and the microcapsule 2, the following were used.

(Microcapsule 1)
-Capsule wall: urea resin-Inclusion agent: 90% by mass of methyl methacrylate monomer as (meth) acrylic monomer, organic peroxide: 10% by mass of benzoyl peroxide
・ Mass ratio (inner capsule / capsule wall): 80/20
・ Average particle size: 60 μm

(Microcapsule 2)
-Capsule wall: urea resin-Encapsulating agent: 90% by mass of methyl methacrylate monomer as (meth) acrylic monomer, 10% by mass of N, N-dimethyl-p-toluidine as tertiary amine
・ Mass ratio (inner capsule / capsule wall): 80/20
・ Average particle size: 60 μm

  The above microcapsules 1 and 2 are prepared by an in-situ polymerization method in which a microcapsule is prepared by dissolving a membrane substance that becomes a capsule wall in a dispersion of a core substance that becomes an encapsulating agent and causing a polymerization reaction at the interface. did. More specifically, microcapsules were prepared in accordance with the method described in paragraphs [0034] to [0039] of Japanese Patent No. 4021858.

  Further, in order to evaluate the characteristics of the obtained powder mixture for powder metallurgy, the powder mixture for powder metallurgy was molded to obtain a green compact. The molding conditions will be described later.

<Example 2>
The mixed powder and green compact for powder metallurgy were the same as in Example 1 except that the amount of microcapsules 1 and 2 added in the secondary addition was 0.5 parts by mass with respect to 100 parts by mass of the iron-based powder. Got.

<Example 3>
A mixed powder for powder metallurgy and a green compact are obtained in the same manner as in Example 1 except that the amount of microcapsules 1 and 2 added in the secondary addition is 1 part by mass with respect to 100 parts by mass of the iron-based powder. It was.

<Example 4>
A mixed powder for powder metallurgy and a green compact were obtained in the same manner as in Example 2 except that the mixing in the secondary addition was performed by heating and mixing at a temperature of 60 ° C. using a high-speed bottom stirring mixer.

<Example 5>
After molding, a mixed powder for powder metallurgy and a green compact were obtained in the same manner as in Example 2 except that a heat curing treatment was further performed at 120 ° C. for 30 minutes.

<Example 6>
The mixed powder for powder metallurgy and the green compact were prepared in the same manner as in Example 2 except that the amount of the copolymerized polyamide particles to be added first was 0.6 parts by mass with respect to 100 parts by mass of the iron-based powder. Obtained.

<Comparative Example 1>
A mixed powder for powder metallurgy and a green compact were obtained in the same manner as in Example 1 except that the secondary addition was not performed. Therefore, microcapsules are not added to the obtained mixed powder for powder metallurgy.

<Comparative Example 2>
A mixed powder for powder metallurgy and a green compact were obtained in the same manner as in Example 1 except that the primary addition was not performed. Therefore, copolymer polyamide is not added to the obtained powder mixture for powder metallurgy.

<Comparative Example 3>
A mixed powder for powder metallurgy and a green compact were obtained in the same manner as in Example 2 except that the primary addition was not performed. Therefore, copolymer polyamide is not added to the obtained powder mixture for powder metallurgy.

<Comparative example 4>
A mixed powder for powder metallurgy and a green compact were obtained in the same manner as in Example 3 except that the primary addition was not performed. Therefore, copolymer polyamide is not added to the obtained powder mixture for powder metallurgy.

<Comparative Example 5>
For powder metallurgy in the same manner as in Comparative Example 1 except that 0.2 parts by mass of ethylene bisstearamide (EBS) was added to 100 parts by mass of the iron-based powder instead of the copolymerized polyamide in the primary addition. Mixed powder and green compact were obtained.

<Comparative Example 6>
Powdered in the same manner as in Example 2 except that 0.2 parts by mass of ethylene bisstearamide (EBS) was added to 100 parts by mass of the iron-based powder instead of the copolymerized polyamide during the primary addition. A metallurgical mixed powder and a green compact were obtained.

<Comparative Example 7>
A mixed powder for powder metallurgy and a green compact were obtained in the same manner as in Example 2 except that the copolymerized polyamide particles to be primarily added were replaced with those having a melting point of 140 ° C. and an average particle size of 40 μm.

<Evaluation>
The following evaluation was performed using the obtained mixed powder for powder metallurgy. Table 1 shows the production conditions and evaluation results of each powder metallurgy mixed powder.

(Fluidity)
50 g of the obtained powder mixture for powder metallurgy was filled in a container having an orifice diameter of 2.5 mm, and the time from filling to discharging was measured to determine the fluidity (unit: sec / 50 g). Other measurement conditions were based on JIS Z 2502: 2012. The fluidity is an index indicating the fluidity of the mixed powder at the time of mold filling, and the smaller the value of the fluidity, the better the fluidity of the mixed powder.

(Density and extraction force)
The obtained mixed powder for powder metallurgy was molded at a molding pressure of 588 MPa in accordance with Japan Powder Metallurgy Industry Association Standard JPMA P10-1992, and the density (unit: g / cm ³ ) of the obtained green compact and The extraction force (unit: MPa) was measured. The lower the extraction force value, the better the extraction performance.

(Folding strength)
The obtained mixed powder for powder metallurgy is molded at a molding pressure of 588 MPa in accordance with Japan Powder Metallurgy Industry Association Standard JPMA P10-1992, and the bending strength (unit: MPa) of the obtained green compact is measured. did. The bending strength of the green compact is a numerical index for cracks that occur during drilling. The larger the bending strength, the higher the green compact strength. It means excellent workability.

  As can be seen from the results shown in Table 1, the mixed powder for powder metallurgy satisfying the conditions of the present invention was excellent in fluidity. In addition, the green compact produced using the mixed powder had excellent drawability and density, and excellent workability even in a state before sintering.

Claims (3)

A powder mixture for powder metallurgy comprising an iron-based powder, a copolymerized polyamide having a melting point of 80 to 120 ° C., a first microcapsule, and a second microcapsule,
The first microcapsule includes a first liquid curable compound,
The second microcapsule includes at least one of a second liquid curable compound different from the first liquid curable compound, a curing agent, and a curing accelerator;
The total content of the first microcapsule and the second microcapsule is 0.5 to 1 part by mass with respect to 100 parts by mass of the iron-based powder,
The mixed powder for powder metallurgy, wherein the content of the liquid curable compound not encapsulated in the microcapsules in the mixed powder for powder metallurgy is 0.10 parts by mass or less with respect to 100 parts by mass of the iron-based powder.   The mixed powder for powder metallurgy according to claim 1, wherein the content of the copolymerized polyamide is 0.05 to 0.4 parts by mass with respect to 100 parts by mass of the iron-based powder. The mixed powder for powder metallurgy according to claim 1 or 2 , wherein the iron-based powder is coated with the copolymerized polyamide.