JP2017071856A - Mixed powder for powder metallurgy - Google Patents
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- 239000011812 mixed powder Substances 0.000 title claims abstract description 58
- 238000004663 powder metallurgy Methods 0.000 title claims abstract description 40
- 239000003094 microcapsule Substances 0.000 claims abstract description 131
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000007788 liquid Substances 0.000 claims abstract description 82
- 239000000843 powder Substances 0.000 claims abstract description 61
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 229910052742 iron Inorganic materials 0.000 claims abstract description 37
- 229940126062 Compound A Drugs 0.000 claims abstract description 35
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Landscapes
- Polymerisation Methods In General (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
本発明は、粉末冶金用混合粉末に関する。 The present invention relates to a mixed powder for powder metallurgy.
粉末冶金は、鉄基粉末等を含む混合粉末を加圧成形して圧粉体を得た後、この圧粉体を焼結させて機械部品などの焼結部品を製造する技術である。 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.
近年、粉末冶金技術の進歩によって、高寸法精度で複雑な形状の焼結部品をニアネット形状に製造できるようになり、各種分野の製品で粉末冶金技術が利用されている。
しかし、焼結部品について、極めて厳しい寸法精度が要求される場合、または、横穴形状、アンダーカット形状、もしくは、その他の高度に複雑な形状が要求される場合には、焼結後の後加工（切削加工など）が必要となることがある。
ところが、焼結部品は、後加工するには強度が高く、また、空孔含有比率が高いことから、切削抵抗および摩擦熱が大きくなり、切削工具の表面温度が上がりやすくなる。そのため、切削工具が損耗しやすくなって短寿命となり、その結果、切削加工費が増大して、焼結部品の製造コストの上昇を招くという問題が生じる。
In recent years, with the progress of powder metallurgy technology, it has become possible to manufacture sintered parts having high dimensional accuracy and complex shapes in a near net shape, and powder metallurgy technology is used in 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 void content ratio, so that cutting resistance and frictional heat increase, and the surface temperature of the cutting tool tends to increase. Therefore, the cutting tool is easily worn out and has a short life, resulting in a problem that the cutting cost is increased and the manufacturing cost of the sintered part is increased.
そこで、上記問題の解決策として、焼結前の圧粉体に切削加工を行ってから焼結を行なう、いわゆるグリーン加工が関心を集めている。
しかし、一般的に焼結前の圧粉体は脆く、加工性が不十分である場合が多い。すなわち、焼結前の圧粉体は、グリーン加工する際の治具への装着時または切削加工時にかかる応力に耐えられず、損傷しやすい。このため、グリーン加工に耐え得るよう、圧粉体の高強度化が望まれている。
圧粉体を高強度化する観点から、例えば、特許文献１には、「熱硬化性樹脂粉末」を含有する粉末冶金用混合粉末が開示されており、これを原料として得られる圧粉体については、「焼結前においても適度な密度と強度を有するために切削加工が可能」とされている（特許文献１の段落［００１５］）。
Therefore, as a solution to the above problem, so-called green processing, in which a green compact before sintering is cut and then 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.
From the viewpoint of increasing the strength of the green compact, for example, Patent Document 1 discloses a mixed powder for powder metallurgy containing “thermosetting resin powder”. Is "Because of having an appropriate density and strength even before sintering, cutting is possible" (paragraph [0015] of Patent Document 1).
上述したように、グリーン加工の観点から、粉末冶金用混合粉末を加圧成形して得られる圧粉体には、焼結前の加工性が優れる（損傷を抑制しながら切削加工等の加工ができる）ことが要求される。 As described above, from the viewpoint of green processing, the green compact obtained by pressure forming the mixed powder for powder metallurgy has excellent workability before sintering (processing such as cutting while suppressing damage). Is possible).
ところで、粉末冶金用混合粉末において、例えば、貯蔵ホッパーからの排出時や金型への充填時などの移送時における粉末冶金用混合粉末の流動性は、生産スピードや充填性に影響を与える重要な特性の一つである。このため、製品品質の向上や製造コスト低減などを実現するためには、粉末冶金用混合粉末が良好な流動性を有することが要求される。
そこで、本発明者らが、特許文献１に記載の粉末冶金用混合粉末について検討したところ、流動性が不十分な場合があることが分かった。
By the way, in the mixed powder for powder metallurgy, for example, the fluidity of the mixed powder for powder metallurgy at the time of transfer such as discharging from the storage hopper or filling into the mold is important to affect the production speed and fillability. One of the characteristics. For this reason, in order to improve product quality, reduce manufacturing costs, etc., it is required that the mixed powder for powder metallurgy has good fluidity.
Then, when the present inventors examined the mixed powder for powder metallurgy described in Patent Document 1, it was found that fluidity may be insufficient.
本発明は、以上の点を鑑みてなされたものであり、流動性が良好であり、かつ、圧粉体にしたときに焼結前の加工性が優れる粉末冶金用混合粉末を提供することを目的とする。 The present invention has been made in view of the above points, and provides a mixed powder for powder metallurgy that has good flowability and excellent workability before sintering when formed into a green compact. Objective.
本発明者らは、鋭意検討した結果、下記構成により上記目的が達成されることを見出し、本発明を完成させた。
すなわち、本発明は、以下の［１］〜［２］を提供する。
［１］鉄基粉末、マイクロカプセル１、および、上記マイクロカプセル１とは異なるマイクロカプセル２を含有し、上記マイクロカプセル１が、液状硬化性化合物Ａを内包し、上記マイクロカプセル２が、上記液状硬化性化合物Ａとは異なる液状硬化性化合物Ｂを内包するか、または、上記マイクロカプセル１が、上記液状硬化性化合物Ａを内包し、上記マイクロカプセル２が、硬化剤および硬化促進剤からなる群から選ばれる少なくとも１種を内包し、マイクロカプセルに内包されていない液状硬化性化合物の含有量が、上記鉄基粉末１００質量部に対して、０．１０質量部以下である、粉末冶金用混合粉末。
［２］上記マイクロカプセル１および上記マイクロカプセル２の合計含有量が、上記鉄基粉末１００質量部に対して、０．０５〜２質量部である、上記［１］に記載の粉末冶金用混合粉末。
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 present invention provides the following [1] to [2].
[1] An iron-based powder, a microcapsule 1 and a microcapsule 2 different from the microcapsule 1 are contained, the microcapsule 1 encapsulates the liquid curable compound A, and the microcapsule 2 is liquid. A group containing a liquid curable compound B different from the curable compound A, or the microcapsule 1 containing the liquid curable compound A, and the microcapsule 2 comprising a curing agent and a curing accelerator. Powder metallurgy mixing, wherein the content of the liquid curable compound encapsulating at least one selected from is not more than 0.10 parts by mass with respect to 100 parts by mass of the iron-based powder. Powder.
[2] The powder metallurgy mixing according to [1], wherein the total content of the microcapsule 1 and the microcapsule 2 is 0.05 to 2 parts by mass with respect to 100 parts by mass of the iron-based powder. Powder.
本発明によれば、流動性が良好であり、かつ、圧粉体にしたときに焼結前の加工性が優れる粉末冶金用混合粉末を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the fluidity | liquidity is favorable and can provide the mixed powder for powder metallurgy which is excellent in the workability before sintering when it is set as a green compact.
［粉末冶金用混合粉末］
本発明の粉末冶金用混合粉末（以下、単に「本発明の混合粉末」ともいう）は、鉄基粉末、マイクロカプセル１、および、上記マイクロカプセル１とは異なるマイクロカプセル２を含有し、上記マイクロカプセル１が、液状硬化性化合物Ａを内包し、上記マイクロカプセル２が、上記液状硬化性化合物Ａとは異なる液状硬化性化合物Ｂを内包するか、または、上記マイクロカプセル１が、上記液状硬化性化合物Ａを内包し、上記マイクロカプセル２が、硬化剤および硬化促進剤からなる群から選ばれる少なくとも１種を内包し、マイクロカプセルに内包されていない液状硬化性化合物の含有量が、上記鉄基粉末１００質量部に対して、０．１０質量部以下である、粉末冶金用混合粉末である。
[Mixed powder for powder metallurgy]
The mixed powder for powder metallurgy of the present invention (hereinafter also simply referred to as “mixed powder of the present invention”) contains an iron-based powder, microcapsules 1 and microcapsules 2 different from the microcapsules 1, The capsule 1 contains the liquid curable compound A, and the microcapsule 2 contains the liquid curable compound B different from the liquid curable compound A, or the microcapsule 1 contains the liquid curable compound A. The compound A is encapsulated, the microcapsule 2 encapsulates at least one selected from the group consisting of a curing agent and a curing accelerator, and the content of the liquid curable compound not encapsulated in the microcapsule is the iron group The mixed powder for powder metallurgy is 0.10 parts by mass or less with respect to 100 parts by mass of the powder.
本発明の混合粉末は、流動性が良好であり、かつ、圧粉体にしたときに焼結前の加工性が優れる。この理由は、以下のように推測される。
まず、本発明の混合粉末を加圧成形して圧粉体を得る際に、マイクロカプセルから液状硬化性化合物が染み出して、鉄基粉末の粒子間に行き渡り、鉄基粉末の粒子どうしが接着される。このため、本発明の混合粉末を加圧成形して得られる圧粉体は、焼結前であっても高強度化され、損傷を抑制しながら切削加工等の加工を行なうことができる（加工性が優れる）と考えられる。
また、本発明の混合粉末は、加圧成形する前の状態では、液状硬化性化合物はマイクロカプセルに内包されており、かつ、マイクロカプセルに内包されていない液状硬化性化合物も実質的に含有していないため、鉄基粉末の粒子どうしが接着されることがなく、流動性に優れると考えられる。
これに対して、硬化性樹脂粉末を含有する粉末冶金用混合粉末（例えば、特許文献１を参照）は、圧粉体にしたときの焼結前の加工性は比較的良好であると考えられるが、加圧成形前においても接着性能が発揮され得るために流動性が劣ると考えられる。
The mixed powder of the present invention has good fluidity and excellent workability before sintering when formed into a green compact. The reason is presumed as follows.
First, when the mixed powder of the present invention is pressure-molded to obtain a green compact, the liquid curable compound exudes from the microcapsule, spreads between the iron-based powder particles, and the iron-based powder particles adhere to each other. Is done. For this reason, 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 (processing) It is considered that the property is excellent.
Further, in the mixed powder of the present invention, the liquid curable compound is encapsulated in the microcapsule and substantially contains the liquid curable compound not encapsulated in the microcapsule before being pressure-molded. Therefore, it is considered that the particles of the iron-based powder are not adhered to each other and have excellent fluidity.
On the other hand, mixed powder for powder metallurgy containing a curable resin powder (see, for example, Patent Document 1) is considered to have relatively good workability before sintering when it is formed into a green compact. However, it is considered that the fluidity is inferior because adhesion performance can be exhibited even before pressure molding.
次に、本発明の混合粉末が含有する各成分について説明する。 Next, each component contained in the mixed powder of the present invention will be described.
〔鉄基粉末〕
鉄基粉末としては、例えば、純鉄粉、合金鋼粉などが挙げられる。
純鉄粉の具体例としては、アトマイズ鉄粉（atomized iron powder）、還元鉄粉（reduced iron powder）などが挙げられる。
合金鋼粉の具体例としては、部分拡散合金化鋼粉、完全合金化鋼粉（合金成分が溶製時より含まれているもの）、完全合金化鋼粉に合金成分を部分拡散させたハイブリッド鋼粉などが挙げられる。合金鋼粉における合金成分としては、例えば、Ｃｒ、Ｍｎ、Ｎｉ、Ｍｏ、Ｖ、Ｔｉ、Ｃｕ、Ｎｂ等が挙げられ、特に、Ｔｉ、Ｎｉ、Ｍｏ、Ｃｕ等は拡散接合によっても添加できる。合金成分の含有量は、鉄基粉末である前提（Ｆｅ：５０質量％以上）を満たせば、特に限定されない。
なお、鉄基粉末中には、例えば合計３質量％程度以下の不純物が含まれていてもよい。代表的な不純物の含有量は、質量％で、Ｃ：０．０５％以下、Ｓｉ：０．１０％以下、Ｍｎ（合金元素として添加しない場合）：０．５０％以下、Ｐ：０．０３％以下、Ｓ：０．０３％以下、Ｏ：０．３０％以下、Ｎ：０．１％以下である。
鉄基粉末の平均粒径は、粉末冶金に用いられる通常の範囲として、７０〜１００μｍにすることが好ましい。なお、鉄基粉末の粒径は、特に断りがない限り、ＪＩＳ Ｚ ２５１０：２００４に準拠した乾式ふるい分けによる測定値とする。
[Iron-based powder]
Examples of the iron-based powder include pure iron powder and alloy steel powder.
Specific examples of the pure iron powder include atomized iron powder and reduced iron powder.
Specific examples of alloy steel powder include partially diffused alloyed steel powder, fully alloyed steel powder (in which alloy components are included from the time of melting), and hybrids in which alloy components are partially diffused into fully alloyed steel powder. Examples include steel powder. Examples of the alloy component in the alloy steel powder include Cr, Mn, Ni, Mo, V, Ti, Cu, and Nb. In particular, Ti, Ni, Mo, Cu, and the like can be added by diffusion bonding. Content of an alloy component will not be specifically limited if the premise (Fe: 50 mass% or more) which is an iron-based powder is satisfy | filled.
The iron-based powder may contain, for example, impurities of about 3% by mass or less in total. Typical impurity content is mass%, C: 0.05% or less, Si: 0.10% or less, Mn (when not added as an alloying element): 0.50% or less, P: 0.03 %: S: 0.03% or less, O: 0.30% or less, N: 0.1% or less.
The average particle size of the iron-based powder is preferably 70 to 100 μm as a normal range used for powder metallurgy. The particle size of the iron-based powder is a measured value by dry sieving based on JIS Z 2510: 2004 unless otherwise specified.
〔マイクロカプセル〕
マイクロカプセルは、膜物質からなるカプセル壁の内部に、内包剤（芯物質）を内包する。
本発明の混合粉末は、マイクロカプセル１と、このマイクロカプセル１とは異なるマイクロカプセル２とを含有する。
そして、本発明においては、マイクロカプセル１が、液状硬化性化合物Ａを内包し、マイクロカプセル２が、液状硬化性化合物Ａとは異なる液状硬化性化合物Ｂを内包するか、または、マイクロカプセル１が、液状硬化性化合物Ａを内包し、マイクロカプセル２が、硬化剤および硬化促進剤からなる群から選ばれる少なくとも１種を内包する。
すなわち、本発明においては、液状硬化性化合物ＡおよびＢがマイクロカプセル化されているため、本発明の混合粉末を加圧成形する前の状態では、鉄基粉末の粒子どうしが接着されることがなく、流動性に優れる。
以下では、便宜的に、マイクロカプセル１および２をまとめて単に「マイクロカプセル」と呼ぶ場合がある。また、液状硬化性化合物ＡおよびＢをまとめて単に「液状硬化性化合物」と呼ぶ場合がある。
[Microcapsule]
A microcapsule encapsulates an encapsulant (core material) inside a capsule wall made of a membrane material.
The mixed powder of the present invention contains a microcapsule 1 and a microcapsule 2 different from the microcapsule 1.
In the present invention, the microcapsule 1 encapsulates the liquid curable compound A and the microcapsule 2 encapsulates the liquid curable compound B different from the liquid curable compound A, or the microcapsule 1 The liquid curable compound A is included, and the microcapsule 2 includes at least one selected from the group consisting of a curing agent and a curing accelerator.
That is, in the present invention, since the liquid curable compounds A and B are microencapsulated, the particles of the iron-based powder may be bonded to each other before the mixed powder of the present invention is pressed. There is no fluidity.
Hereinafter, for convenience, the microcapsules 1 and 2 may be simply referred to as “microcapsules”. Further, the liquid curable compounds A and B may be collectively referred to simply as “liquid curable compound”.
なお、本明細書において、「液状」とは、常温（２５℃）で液体であることを意味する。同様に、「粉末状」とは、常温で固体であることを意味する。 In this specification, “liquid” means liquid at normal temperature (25 ° C.). Similarly, “powdered” means solid at room temperature.
液状硬化性化合物などをマイクロカプセル化する方法としては、特に限定されず、従来公知の方法を使用でき、例えば、Ｓ／Ｏマイクロカプセル法、相分離法、界面重合法、ｉｎ−ｓｉｔｕ重合法、スプレードライ法などが挙げられるが、これらの方法に限定されない。
なお、ｉｎ−ｓｉｔｕ重合法は、内包剤となる芯物質の分散溶液中に、カプセル壁となる膜物質を溶解し、界面で重合反応を起こすことにより、マイクロカプセルを調製する方法であり、具体的には、例えば、特開２００５−２３０６８７号公報の段落［００３４］〜［００３９］に記載された方法が挙げられるが、この方法に限定されない。
A method for microencapsulating a liquid curable compound or the like is not particularly limited, and a conventionally known method can be used. For example, an S / O microcapsule method, a phase separation method, an interfacial polymerization method, an in-situ polymerization method, Examples thereof include a spray drying method, but are not limited to these methods.
The in-situ polymerization method is a method of preparing a microcapsule by dissolving a membrane substance that becomes a capsule wall in a dispersion solution of a core substance that becomes an encapsulating agent and causing a polymerization reaction at the interface. Specifically, for example, the method described in paragraphs [0034] to [0039] of JP-A-2005-230687 can be mentioned, but the method is not limited thereto.
また、マイクロカプセルのカプセル壁の材質（カプセル壁材）としては、特に限定されず、従来公知の樹脂が使用でき、例えば、尿素樹脂、メラミン−ホルムアルデヒド樹脂、ポリエステル樹脂、スチレンアクリル樹脂などが挙げられるが、これらの樹脂に限定されない。
マイクロカプセルにおいて、内包剤とカプセル壁との質量比（内包剤／カプセル壁）は、特に限定されないが、例えば、９９／１〜５０／５０であり、９５／５〜７０／３０が好ましい。
The material of the capsule wall of the microcapsule (capsule wall material) is not particularly limited, and conventionally known resins can be used, and examples thereof include urea resin, melamine-formaldehyde resin, polyester resin, styrene acrylic resin, and the like. However, it is not limited to these resins.
In the microcapsule, the mass ratio between the encapsulating agent and the capsule wall (encapsulating agent / capsule wall) is not particularly limited, and is, for example, 99/1 to 50/50, and preferably 95/5 to 70/30.
なお、粉末冶金用混合粉末は、加圧成形後における抜出し性を良好にするため、通常、潤滑剤（離型剤）が配合されることが多いが、本発明の混合粉末においては、マイクロカプセルを含有することで、抜出し性を良好にできる。もっとも、本発明の混合粉末に潤滑剤を配合することは排除されない。 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. By including the extractability can be improved. However, blending a lubricant with the mixed powder of the present invention is not excluded.
上述したように、本発明においては、マイクロカプセル１が、液状硬化性化合物Ａを内包し、マイクロカプセル２が、液状硬化性化合物Ａとは異なる液状硬化性化合物Ｂを内包するか、または、マイクロカプセル１が、液状硬化性化合物Ａを内包し、マイクロカプセル２が、硬化剤および硬化促進剤からなる群から選ばれる少なくとも１種を内包する。
本発明の混合粉末を加圧成形して圧粉体を得る際に、マイクロカプセル１および２から内包剤が染み出して、鉄基粉末の粒子どうしを接着する。
マイクロカプセル１および２の内包剤である液状硬化性化合物ＡおよびＢ、硬化剤ならびに硬化促進剤としては、特に限定されず、接着剤等として従来公知の液状硬化性化合物、硬化剤および硬化促進剤を適宜使用できる。
As described above, in the present invention, the microcapsule 1 encloses the liquid curable compound A and the microcapsule 2 encloses the liquid curable compound B different from the liquid curable compound A, or the microcapsule 2 The capsule 1 includes the liquid curable compound A, and the microcapsule 2 includes at least one selected from the group consisting of a curing agent and a curing accelerator.
When pressing the mixed powder of the present invention to obtain a green compact, the encapsulant oozes out from the microcapsules 1 and 2, and the particles of the iron-based powder are bonded to each other.
There are no particular limitations on the liquid curable compounds A and B, which are the encapsulating agents for the microcapsules 1 and 2, the curing agent and the curing accelerator, and conventionally known liquid curable compounds, curing agents and curing accelerators such as adhesives and the like. Can be used as appropriate.
なお、マイクロカプセル１および２は、上記必須成分を内包していれば、更に、その他の成分を内包していてもよい。
以下に、マイクロカプセル１および２の内包剤の例を記載する。以下の例示では、便宜的に、液状硬化性化合物Ａの硬化剤を「硬化剤Ａ」と表記し、液状硬化性化合物Ａの硬化促進剤を「硬化促進剤Ａ」と表記する。液状硬化性化合物Ｂの硬化剤および硬化促進剤についても同様に表記する。
The microcapsules 1 and 2 may further include other components as long as they include the essential components.
Below, the example of the encapsulating agent of the microcapsules 1 and 2 is described. In the following examples, for convenience, the curing agent of the liquid curable compound A is denoted as “curing agent A”, and the curing accelerator of the liquid curable compound A is denoted as “curing accelerator A”. The same applies to the curing agent and curing accelerator of the liquid curable compound B.
マイクロカプセル１の内包剤としては、例えば、１）液状硬化性化合物Ａ、２）液状硬化性化合物Ａおよび硬化剤Ａ、３）液状硬化性化合物Ａおよび硬化剤Ｂ、４）液状硬化性化合物Ａ、硬化剤Ａおよび硬化剤Ｂ、５）液状硬化性化合物Ａ、硬化促進剤Ａおよび硬化促進剤Ｂ、などが挙げられる。
なお、上記３）〜５）は、マイクロカプセル２が液状硬化性化合物Ｂを内包する場合の例である。
Examples of the encapsulating agent for the microcapsule 1 include 1) liquid curable compound A, 2) liquid curable compound A and curing agent A, 3) liquid curable compound A and curing agent B, and 4) liquid curable compound A. , Curing agent A and curing agent B, 5) liquid curable compound A, curing accelerator A and curing accelerator B, and the like.
In addition, said 3) -5) is an example in case the microcapsule 2 encloses the liquid curable compound B. FIG.
このとき、マイクロカプセル２の内包剤としては、例えば、ｉ）液状硬化性化合物Ｂ、ii）液状硬化性化合物Ｂ、硬化促進剤Ａおよび硬化促進剤Ｂ、iii）硬化剤Ａ、iv）硬化剤Ａおよび硬化促進剤Ａ、ｖ）硬化促進剤Ａ、vi）液状硬化性化合物Ａおよび硬化促進剤Ａ、などが挙げられる。 At this time, as the encapsulating agent of the microcapsule 2, for example, i) liquid curable compound B, ii) liquid curable compound B, curing accelerator A and curing accelerator B, iii) curing agent A, iv) curing agent A and curing accelerator A, v) curing accelerator A, vi) liquid curable compound A and curing accelerator A, and the like.
なお、上記例において、硬化剤Ａおよび硬化剤Ｂは同一であってもよく、硬化促進剤Ａおよび硬化促進剤Ｂも、同一であってよい。 In the above example, the curing agent A and the curing agent B may be the same, and the curing accelerator A and the curing accelerator B may be the same.
このような内包剤としては、例えば、ウレタン系、エポキシ系、（メタ）アクリル系、変成シリコーン系（エポキシ・変成シリコーン系、アクリル・変成シリコーン系などを含む）などの内包剤が挙げられるが、これらに限定されるものではない。ここで、「（メタ）アクリル」は「アクリルおよび／またはメタクリル」を意味する。 Examples of such encapsulating agents include urethane-based, epoxy-based, (meth) acrylic-based, modified silicone-based (including epoxy-modified silicone-based, acrylic-modified silicone-based, etc.), It is not limited to these. Here, “(meth) acryl” means “acryl and / or methacryl”.
ウレタン系の場合、例えば、液状硬化性化合物Ａとしてポリオールをマイクロカプセル１に内包させ、液状硬化性化合物Ｂとしてウレタンプレポリマーまたは硬化剤としてポリイソシアネートをマイクロカプセル２に内包させる。このとき、一例として、マイクロカプセル２に内包させる硬化剤の含有量は、マイクロカプセル１に内包させる液状硬化性化合物Ａとマイクロカプセル２に内包させる液状硬化性化合物Ｂとの合計量を１００質量部としたとき、３〜２０質量部程度であることが好ましい。 In the case of urethane, for example, a polyol is encapsulated in the microcapsule 1 as the liquid curable compound A, and a polyisocyanate is encapsulated in the microcapsule 2 as the urethane prepolymer or the curing agent as the liquid curable compound B. At this time, as an example, the content of the curing agent included in the microcapsule 2 is 100 parts by mass of the total amount of the liquid curable compound A included in the microcapsule 1 and the liquid curable compound B included in the microcapsule 2. When it is, it is preferable that it is about 3-20 mass parts.
エポキシ系の場合、例えば、液状硬化性化合物Ａとしてエポキシ樹脂プレポリマーをマイクロカプセル１に内包させ、硬化剤として脂肪酸ポリアミンおよび硬化促進剤として第三級アミンをマイクロカプセル２に内包させる。このとき、内包剤の質量比（エポキシ樹脂プレポリマー：硬化剤：硬化促進剤）は、５０〜９０：５〜４０：０．１〜２０が好ましい。また、マイクロカプセルの質量比（マイクロカプセル１／マイクロカプセル２）は、５０／５０〜９９．９／０．１が好ましい。 In the case of an epoxy system, for example, an epoxy resin prepolymer is encapsulated in the microcapsule 1 as the liquid curable compound A, and a fatty acid polyamine as a curing agent and a tertiary amine as a curing accelerator is encapsulated in the microcapsule 2. At this time, the mass ratio of the encapsulating agent (epoxy resin prepolymer: curing agent: curing accelerator) is preferably 50 to 90: 5 to 40: 0.1 to 20. The mass ratio of microcapsules (microcapsule 1 / microcapsule 2) is preferably 50/50 to 99.9 / 0.1.
（メタ）アクリル系の場合、例えば、液状硬化性化合物Ａとして（メタ）アクリルモノマー９０〜９９．９質量％および硬化剤として有機過酸化物０．１〜１０質量％をマイクロカプセル１に内包させ、硬化促進剤として第三級アミンをマイクロカプセル２に内包させる。このとき、マイクロカプセルの質量比（マイクロカプセル１／マイクロカプセル２）は、９０／１０〜９９．９／０．１が好ましい。 In the case of (meth) acrylic, for example, 90 to 99.9% by mass of (meth) acrylic monomer as liquid curable compound A and 0.1 to 10% by mass of organic peroxide as curing agent are included in microcapsule 1. Then, a tertiary amine is included in the microcapsule 2 as a curing accelerator. At this time, the mass ratio of microcapsules (microcapsule 1 / microcapsule 2) is preferably 90/10 to 99.9 / 0.1.
また、（メタ）アクリル系の場合、他には、例えば、液状硬化性化合物Ａとして（メタ）アクリルモノマー９０〜９９．９質量％および硬化剤として有機過酸化物０．１〜１０質量％をマイクロカプセル１に内包させ、液状硬化性化合物Ｂとして（メタ）アクリルモノマー９０〜９９．９５質量％および（メタ）アクリルモノマーの還元剤として可溶性バナジウム化合物０．０５〜１０質量％をマイクロカプセル２に内包させる。（メタ）アクリルモノマーは、液状硬化性化合物ＡとＢとで同じであってもよい。このとき、マイクロカプセルの質量比（マイクロカプセル１／マイクロカプセル２）は、５０／５０〜９９．９／０．１が好ましい。 In the case of the (meth) acrylic type, for example, 90 to 99.9% by mass of (meth) acrylic monomer as the liquid curable compound A and 0.1 to 10% by mass of organic peroxide as the curing agent are used. The microcapsule 1 is encapsulated, and 90 to 99.95% by mass of (meth) acrylic monomer as liquid curable compound B and 0.05 to 10% by mass of soluble vanadium compound as a reducing agent for (meth) acrylic monomer are contained in microcapsule 2. Enclose. The (meth) acrylic monomer may be the same for the liquid curable compounds A and B. At this time, the mass ratio of microcapsules (microcapsule 1 / microcapsule 2) is preferably 50/50 to 99.9 / 0.1.
更に、（メタ）アクリル系の場合、例えば、液状硬化性化合物Ａとして（メタ）アクリルモノマー９０〜９９．９質量％および硬化剤として有機過酸化物０．１〜１０質量％をマイクロカプセル１に内包させ、液状硬化性化合物Ｂとして（メタ）アクリルモノマー９０〜９９．９質量％および硬化促進剤として第三級アミン０．１〜１０質量％をマイクロカプセル２に内包させる。（メタ）アクリルモノマーは、液状硬化性化合物ＡとＢとで同じであってもよい。このとき、マイクロカプセルの質量比（マイクロカプセル１／マイクロカプセル２）は、５０／５０〜９９．９／０．１が好ましい。 Further, in the case of the (meth) acrylic type, for example, 90 to 99.9% by mass of (meth) acrylic monomer as the liquid curable compound A and 0.1 to 10% by mass of organic peroxide as the curing agent are contained in the microcapsule 1. The microcapsule 2 encapsulates 90 to 99.9% by mass of (meth) acrylic monomer as the liquid curable compound B and 0.1 to 10% by mass of tertiary amine as the curing accelerator. The (meth) acrylic monomer may be the same for the liquid curable compounds A and B. At this time, the mass ratio of microcapsules (microcapsule 1 / microcapsule 2) is preferably 50/50 to 99.9 / 0.1.
ここで、（メタ）アクリルモノマーとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ドデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベヘニル（メタ）アクリレートなどのアルキル（メタ）アクリレート類；２−ヒドロキシエチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレートなどのヒドロキシアルキル（メタ）アクリレート類；グリシジル（メタ）アクリレート、グリシジルアルキル（メタ）アクリレートなどのグリシジル（メタ）アクリレート類；アルコキシアルキル（メタ）アクリレート類；アリル（メタ）アクリレート、アリルアルキル（メタ）アクリレートなどのアリルアルキル（メタ）アクリレート類；モノエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレートなどの多官能性（メタ）アクリレート類；等が挙げられるが、これらに限定されない。
また、第三級アミンとしては、例えば、キノリン、メチルキノリン、キナルジン、キノキサリン、フェナジンなどの複素環第三級アミン；Ｎ，Ｎ−ジメチル−アニシジン、Ｎ，Ｎ−ジメチルアニリン，Ｎ，Ｎ−ジメチル−ｐ−トルイジンなどの芳香族第三級アミン類；等が挙げられるが、これらに限定されない。
また、有機過酸化物としては、例えば、クメンハイドロパーオキサイド、ｔ−ブチルハイドロパーオキサイド、ｐ−メタンハイドロパーオキサイド、メチルエチルケトンパーオキサイド、シクロヘキサンパーオキサイド、ジクミルパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイドなどのハイドロパーオキサイド；ケトンパーオキサイド類；ジアリルパーオキサイド類；パーオキシエステル類；等が挙げられるが、これらに限定されない。
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) acrylate. Alkyl (meth) acrylates such as 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 (meth) acrylate Allylalkyl (meth) acrylates such as relate; Multifunctional (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.
Examples of the organic peroxide include cumene hydroperoxide, t-butyl hydroperoxide, p-methane hydroperoxide, methyl ethyl ketone peroxide, cyclohexane peroxide, dicumyl peroxide, and diisopropylbenzene hydroperoxide. Hydroperoxides; Ketone peroxides; Diallyl peroxides; Peroxyesters; and the like, but are not limited to these.
変成シリコーン樹脂系の場合、例えば、液状硬化性化合物Ａとして変成シリコーン樹脂９０〜９９質量％および硬化剤として脂肪酸ポリアミン１〜１０質量％をマイクロカプセル１に内包させ、液状硬化性化合物Ｂとしてエポキシ樹脂９０〜９９．９質量％および硬化促進剤として有機錫０．１〜１０質量％をマイクロカプセル２に内包させる。このとき、マイクロカプセルの質量比（マイクロカプセル１／マイクロカプセル２）は、５０／５０〜９９．９／０．１が好ましい。 In the case of the modified silicone resin system, for example, 90 to 99% by mass of the modified silicone resin as the liquid curable compound A and 1 to 10% by mass of the fatty acid polyamine as the curing agent are encapsulated in the microcapsule 1, and the epoxy resin as the liquid curable compound B 90 to 99.9% by mass and 0.1 to 10% by mass of organic tin as a curing accelerator are encapsulated in the microcapsule 2. At this time, the mass ratio of microcapsules (microcapsule 1 / microcapsule 2) is preferably 50/50 to 99.9 / 0.1.
上述した液状硬化性化合物の分子量（重量平均分子量、数平均分子量を含む）は、液状であれば特に限定されず、適宜設定される。 The molecular weight (including the weight average molecular weight and the number average molecular weight) of the liquid curable compound described above is not particularly limited as long as it is liquid, and is appropriately set.
〈マイクロカプセルの平均粒径〉
マイクロカプセル１および２の平均粒径は、大きすぎると本発明の混合粉末の密度が低下して目的の強度が得られにくくなる場合があり、小さすぎると流動性が不十分となる場合があることから、５〜１００μｍが好ましく、２０〜９０μｍがより好ましく、３０〜８０μｍが更に好ましい。マイクロカプセルの平均粒径がこの範囲であれば、本発明の混合粉末は、流動性がより良好となり、圧粉体にしたときの焼結前の加工性がより優れる。
なお、マイクロカプセルの平均粒径は、レーザー回折／散乱式粒度分布計を用いて測定することができ、体積平均粒子径をいう。
<Average particle size of microcapsules>
If the average particle size of the microcapsules 1 and 2 is too large, the density of the mixed powder of the present invention may be reduced and it may be difficult to obtain the desired strength, and if it is too small, the fluidity may be insufficient. Therefore, 5 to 100 μm is preferable, 20 to 90 μm is more preferable, and 30 to 80 μm is still more preferable. When the average particle diameter of the microcapsules is within this range, the mixed powder of the present invention has better fluidity and better workability before sintering when it is formed into a green compact.
In addition, the average particle diameter of a microcapsule can be measured using a laser diffraction / scattering particle size distribution meter, and refers to a volume average particle diameter.
〈マイクロカプセルの含有量〉
本発明の混合粉末におけるマイクロカプセル１および２の合計含有量は、少なすぎると加圧成形時に内包剤が十分に染み出さず、十分な強度が得られにくい場合があり、多すぎると鉄基粉末の粒子どうしのネッキングを阻害して強度が低下する場合があり得ることから、鉄基粉末１００質量部に対して、０．０５〜２質量部が好ましく、０．０８〜１．５質量部がより好ましく、０．１０〜１．０質量部が更に好ましい。
<Content of microcapsules>
If the total content of the microcapsules 1 and 2 in the mixed powder of the present invention is too small, the encapsulating agent may not sufficiently bleed out during pressure molding, and sufficient strength may be difficult to obtain. 0.05-2 parts by mass is preferable with respect to 100 parts by mass of the iron-based powder, and 0.08-1.5 parts by mass is preferable. More preferred is 0.10 to 1.0 part by mass.
〔その他の添加剤〕
本発明の混合粉末は、必要に応じて、その他の添加剤を任意で含有することができる。
例えば、本発明の混合粉末は、マイクロカプセルに内包されていない、硬化剤、硬化促進剤、可塑剤、およびカップリング剤からなる群から選ばれる少なくとも１種を含有できる。これらは、液状であっても粉末状であってもよい。
また、添加剤として潤滑剤を含有してもよく、その具体例としては、金属石鹸（ステアリン酸亜鉛など）、アミドワックス、ポリアミド、ポリエチレン、酸化ポリエチレン等が挙げられる。
[Other additives]
The mixed powder of the present invention can optionally contain other additives as necessary.
For example, the mixed powder of the present invention can contain at least one selected from the group consisting of a curing agent, a curing accelerator, a plasticizer, and a coupling agent that is not encapsulated in microcapsules. These may be liquid or powdery.
Further, a lubricant may be contained as an additive, and specific examples thereof include metal soap (such as zinc stearate), amide wax, polyamide, polyethylene, polyethylene oxide and the like.
〔マイクロカプセルに内包されていない液状硬化性化合物〕
本発明の混合粉末は、マイクロカプセルに内包されていない液状硬化性化合物の含有量が、鉄基粉末１００質量部に対して、０．１０質量部以下であり、０．０１質量部以下が好ましく、マイクロカプセルに内包されていない液状硬化性化合物を実質的に含有しない態様が更に好ましい。
これにより、本発明の混合粉末を加圧成形する前の状態では、鉄基粉末の粒子どうしが接着されることがなく、流動性に優れる。
なお、マイクロカプセルに内包されていない液状硬化性化合物としては、例えば、マイクロカプセルの内包剤である液状硬化性化合物として説明したものが挙げられる。
本発明においては、マイクロカプセルに内包されていない液状硬化性化合物を粉末冶金用混合粉末に添加しない態様を、「マイクロカプセルに内包されていない液状硬化性化合物を実質的に含有しない態様」とする。
[Liquid curable compound not encapsulated in microcapsules]
In the mixed powder of the present invention, the content of the liquid curable compound not encapsulated in the microcapsule is 0.10 parts by mass or less, preferably 0.01 parts by mass or less with respect to 100 parts by mass of the iron-based powder. Further preferred is an embodiment which does not substantially contain a liquid curable compound not encapsulated in microcapsules.
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.
Examples of the liquid curable compound that is not encapsulated in the microcapsule include those described as the liquid curable compound that is the encapsulating agent of the microcapsule.
In the present invention, a mode in which a liquid curable compound not encapsulated in microcapsules is not added to the powder mixture for powder metallurgy is referred to as “a mode that substantially does not contain a liquid curable compound not encapsulated in microcapsules”. .
〔粉末冶金用混合粉末の製造方法および使用方法〕
本発明の混合粉末は、上述した必須成分および任意成分を、例えば従来公知の混合機を用いて、適宜混合することにより得られる。
このようにして得られた本発明の混合粉末は、粉末冶金の原料として使用できる。すなわち、本発明の混合粉末を、一般的な方法によって、加圧成形して圧粉体（圧粉成形体）とし、次いで、この圧粉体を例えば１０００〜１３００℃で焼結させることで、機械部品などの焼結部品を製造できる。
[Production method and usage of mixed powder for powder metallurgy]
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 conventionally known mixer.
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 pressed into a green compact (a green compact) by a general method, and then the green compact is sintered at 1000 to 1300 ° C., for example. Sintered parts such as machine parts can be manufactured.
このとき、本発明の混合粉末は、加圧成形するに際して、貯蔵ホッパーからの排出時や金型への充填時などの移送時における流動性が優れるため、生産スピードや充填性が良好となり、製品品質の向上や製造コスト低減などが期待できる。
また、本発明の混合粉末を加圧成形して得られた圧粉体は、高強度化されており、焼結前であっても、損傷を抑制しつつ切削加工等の加工（グリーン加工）を行なうことができる。
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 has high strength, and even before sintering, processing such as cutting (green processing) while suppressing damage. Can be performed.
〔加熱硬化処理〕
例えば、（メタ）アクリル系、および、エポキシ系などの内包剤を使用した場合には、加圧成形して得られた圧粉体に対して、焼結前に、内包剤における液状硬化性化合物を硬化させるための加熱硬化処理を行ってもよい。液状硬化性化合物を硬化させることによって、圧粉体の強度を更に向上させることができる。
加熱硬化処理の条件は、使用する液状硬化性化合物（熱硬化性化合物）の種類に応じて決定すればよい。例えば、加熱硬化処理における加熱温度は、一般的には、８０〜２００℃である。また、加熱硬化処理における加熱時間は、例えば、１０分間から１時間であり、１５〜３０分間が好ましい。
[Heat curing]
For example, when an (meth) acrylic and epoxy-based inclusion is used, the liquid curable compound in the inclusion before the sintering of the green compact obtained by pressure molding You may perform the heat-hardening process for hardening. The strength of the green compact can be further improved by curing the liquid curable compound.
What is necessary is just to determine the conditions of a heat-hardening process according to the kind of liquid curable compound (thermosetting compound) to be used. For example, the heating temperature in the heat curing process is generally 80 to 200 ° C. The heating time in the heat curing treatment is, for example, 10 minutes to 1 hour, and preferably 15 to 30 minutes.
以下に、実施例を挙げて本発明を具体的に説明する。ただし、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
＜実施例１および５＞
純鉄粉（ＪＦＥスチール社製 アトマイズ鉄粉３０１Ａ）に銅粉：２質量％および黒鉛粉：０．８質量％を添加した鉄基粉末を準備し、この鉄基粉末１００質量部に対して、液状硬化性化合物Ａとして（メタ）アクリルモノマー９０質量％と硬化剤として有機過酸化物１０質量％とを内包するマイクロカプセル１（詳細は後述）と、液状硬化性化合物Ｂとして（メタ）アクリルモノマー９０質量％と硬化促進剤として第三級アミン１０質量％とを内包するマイクロカプセル２（詳細は後述）とを、１：１の割合（質量比）で、０．５質量部添加し、Ｖ型ブレンダで１５分間混合して、粉末冶金用混合粉末を得た。
なお、実施例１と実施例５との違いは、後述するように、圧粉体に対する加熱硬化処理の有無の違いである。
<Examples 1 and 5>
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. Microcapsule 1 (details will be described later) containing 90% by mass of (meth) acrylic monomer as liquid curable compound A and 10% by mass of organic peroxide as curing agent, and (meth) acrylic monomer as liquid curable compound B Add 0.5 parts by mass of 90% by mass and microcapsule 2 containing 10% by mass of tertiary amine as a curing accelerator (details will be described later) at a ratio (mass ratio) of 1: 1. The mixture was mixed for 15 minutes with a mold blender to obtain a mixed powder for powder metallurgy.
In addition, the difference between Example 1 and Example 5 is a difference of the presence or absence of the heat-hardening process with respect to a green compact so that it may mention later.
・マイクロカプセル１…平均粒径：６０μｍ、カプセル壁：尿素樹脂、（メタ）アクリルモノマー：メタクリル酸メチルモノマー、有機過酸化物：過酸化ベンゾイル、質量比（内包剤／カプセル壁）：８０／２０
・マイクロカプセル２…平均粒径：６０μｍ、カプセル壁：尿素樹脂、（メタ）アクリルモノマー：メタクリル酸メチルモノマー、第三級アミン：Ｎ，Ｎ−ジメチル−ｐ−トルイジン、質量比（内包剤／カプセル壁）：８０／２０
Microcapsule 1: average particle diameter: 60 μm, capsule wall: urea resin, (meth) acrylic monomer: methyl methacrylate monomer, organic peroxide: benzoyl peroxide, mass ratio (encapsulating agent / capsule wall): 80/20
Microcapsule 2 ... average particle diameter: 60 μm, capsule wall: urea resin, (meth) acrylic monomer: methyl methacrylate monomer, tertiary amine: N, N-dimethyl-p-toluidine, mass ratio (encapsulating agent / capsule Wall): 80/20
なお、上記マイクロカプセル１および２は、いずれも、内包剤となる芯物質の分散溶液中に、カプセル壁となる膜物質を溶解し、界面で重合反応を起こすことにより、マイクロカプセルを調製する、ｉｎ−ｓｉｔｕ重合法により作製した。
ｉｎ−ｓｉｔｕ重合法は、上述したように、例えば、特開２００５−２３０６８７号公報の段落［００３４］〜［００３９］に記載された方法が例として挙げられるが、マイクロカプセルの製造方法は、特に限定されず、ｉｎ−ｓｉｔｕ重合法以外にも、通常使用される方法が適用できた。
Each of the microcapsules 1 and 2 prepares microcapsules by dissolving a membrane substance that becomes a capsule wall in a dispersion solution of a core substance that becomes an encapsulating agent and causing a polymerization reaction at the interface. It produced by the in-situ polymerization method.
Examples of the in-situ polymerization method include the methods described in paragraphs [0034] to [0039] of Japanese Patent Application Laid-Open No. 2005-230687, as described above. It is not limited, The method used normally can be applied besides the in-situ polymerization method.
＜実施例２＞
鉄基粉末１００質量部に対して、マイクロカプセル１とマイクロカプセル２とを、１：１の割合（質量比）で、０．７質量部添加した以外は、実施例１と同様にして、粉末冶金用混合粉末を得た。
<Example 2>
The powder was obtained in the same manner as in Example 1 except that 0.7 parts by mass of the microcapsule 1 and the microcapsule 2 were added at a ratio of 1: 1 (mass ratio) to 100 parts by mass of the iron-based powder. A mixed powder for metallurgy was obtained.
＜実施例３＞
鉄基粉末１００質量部に対して、マイクロカプセル１とマイクロカプセル２とを、１：１の割合（質量比）で、０．９質量部添加した以外は、実施例１と同様にして、粉末冶金用混合粉末を得た。
<Example 3>
Powder was obtained in the same manner as in Example 1, except that 0.9 part by mass of microcapsule 1 and microcapsule 2 was added at a ratio (mass ratio) of 1: 1 with respect to 100 parts by mass of iron-based powder. A mixed powder for metallurgy was obtained.
＜実施例４＞
鉄基粉末１００質量部に対して、マイクロカプセル１とマイクロカプセル２とを、１：１の割合（質量比）で、１．０質量部添加した以外は、実施例１と同様にして、粉末冶金用混合粉末を得た。
<Example 4>
The powder was obtained in the same manner as in Example 1 except that 1.0 part by mass of the microcapsule 1 and the microcapsule 2 was added at a ratio of 1: 1 (mass ratio) to 100 parts by mass of the iron-based powder. A mixed powder for metallurgy was obtained.
＜標準例１＞
実施例１で準備した鉄基粉末（ＪＦＥスチール社製 アトマイズ鉄粉３０１Ａに、銅粉：２質量％および黒鉛粉：０．８質量％を添加した鉄基粉末）１００質量部に対して、ステアリン酸亜鉛を１質量部添加し、混合して、粉末冶金用混合粉末を得た。
<Standard example 1>
For 100 parts by mass of iron-based powder prepared in Example 1 (iron-based powder obtained by adding 2% by mass of copper powder and 0.8% by mass of graphite powder to atomized iron powder 301A manufactured by JFE Steel), stearin 1 part by mass of zinc acid was added and mixed to obtain a mixed powder for powder metallurgy.
＜標準例２＞
実施例１で準備した鉄基粉末（ＪＦＥスチール社製 アトマイズ鉄粉３０１Ａに、銅粉：２質量％および黒鉛粉：０．８質量％を添加した鉄基粉末）のみを、標準例２の粉末冶金用混合粉末とした。
<Standard example 2>
Only the iron-based powder prepared in Example 1 (iron-based powder obtained by adding 2% by mass of copper powder and 0.8% by mass of graphite powder to atomized iron powder 301A manufactured by JFE Steel Co., Ltd.) A mixed powder for metallurgy was obtained.
＜比較例１＞
マイクロカプセル１および２に代えて、クリア粉体塗料（商品名：コナックＮｏ．４６００、日本油脂ＢＡＳＦコーティング社製、グリシジル基を側鎖に有するアクリル樹脂を二塩基酸で架橋したもの）を、鉄基粉末１００質量部に対して０．７５質量部添加し、かつ、ステアリン酸亜鉛を鉄基粉末１００質量部に対して０．３質量部添加した以外は、実施例１と同様にして、粉末冶金用混合粉末を得た。
<Comparative Example 1>
Instead of microcapsules 1 and 2, a clear powder coating (trade name: Konak No. 4600, manufactured by NOF BASF Co., Ltd., crosslinked with an acrylic resin having a glycidyl group in the side chain with a dibasic acid), iron Powder was added in the same manner as in Example 1 except that 0.75 part by mass was added to 100 parts by mass of the base powder and 0.3 part by mass of zinc stearate was added to 100 parts by mass of the iron base powder. A mixed powder for metallurgy was obtained.
＜比較例２＞
実施例１で準備した鉄基粉末１００質量部に対して、液状のエポキシ樹脂プレポリマーを内包するマイクロカプセル（詳細は後述）と、粉末状の硬化剤である芳香族アミン（メタフェニレンジアミン）とを、４：１の割合（質量比）で０．５質量部添加し、Ｖ型ブレンダで１５分間混合して、粉末冶金用混合粉末を得た。
そして、得られた粉末冶金用混合粉末に、液状エポキシ樹脂（商品名：エピコート８２８、油化シェルエポキシ社製）を、鉄基粉末１００質量部に対して０．２０質量部添加し混合したものを、比較例２の粉末冶金用混合粉末とした。
・マイクロカプセル…平均粒径：６０μｍ、カプセル壁：尿素樹脂、液状のエポキシ樹脂プレポリマー：ビスフェノールＡ型エポキシ樹脂、質量比（内包剤／カプセル壁）：８０／２０
なお、上記マイクロカプセルは、内包剤となる芯物質の分散溶液中に、カプセル壁となる膜物質を溶解し、界面で重合反応を起すことで、マイクロカプセルを調製する、ｉｎ−ｓｉｔｕ重合法により作製した。より詳細には、特許第５２３９７８６号公報の段落［０１４４］に記載された方法に準拠して、マイクロカプセルを作製した。
<Comparative example 2>
For 100 parts by mass of the iron-based powder prepared in Example 1, a microcapsule (details will be described later) encapsulating a liquid epoxy resin prepolymer, an aromatic amine (metaphenylenediamine) that is a powdery curing agent, Was added in a ratio of 4: 1 (mass ratio) by 0.5 parts by mass, and mixed with a V-type blender for 15 minutes to obtain a mixed powder for powder metallurgy.
Then, 0.20 parts by mass of a liquid epoxy resin (trade name: Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.) is added to 100 parts by mass of the iron-based powder and mixed with the obtained powder metallurgy mixed powder. Was a mixed powder for powder metallurgy of Comparative Example 2.
-Microcapsules: average particle diameter: 60 μm, capsule wall: urea resin, liquid epoxy resin prepolymer: bisphenol A type epoxy resin, mass ratio (encapsulant / capsule wall): 80/20
The above microcapsules are prepared by dissolving the membrane material that becomes the capsule wall in the dispersion solution of the core material that becomes the encapsulating agent, and causing the polymerization reaction at the interface to prepare the microcapsules by an in-situ polymerization method. Produced. More specifically, microcapsules were produced according to the method described in paragraph [0144] of Japanese Patent No. 5239786.
＜評価＞
得られた粉末冶金用混合粉末を用いて、以下の評価を行なった。結果を下記表１に示す。なお、評価を行なわなかった場合には、下記表１に「−」を記載した。
<Evaluation>
The following evaluation was performed using the obtained mixed powder for powder metallurgy. The results are shown in Table 1 below. In addition, when evaluation was not performed, "-" was described in Table 1 below.
（流動度）
流動度は、金型充填時の粉末の流動性を示す指標である。
得られた粉末冶金用混合粉末：５０ｇを、オリフィス径：２．５ｍｍの容器に充填し、充填してから排出するまでの時間を測定して、流動度（単位：ｓｅｃ／５０ｇ）を求めた。なお、その他の測定条件は、ＪＩＳＺ２５０２：２０１２に準拠した。流動度の値が小さいほど流動性に優れるものとして評価できる。
(Fluidity)
The fluidity is an index indicating the fluidity of the powder when filling the mold.
The obtained powder mixture for powder metallurgy: 50 g was filled in a container having an orifice diameter: 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 JISZ2502: 2012. The smaller the fluidity value, the better the fluidity.
（密度および抜出し力）
得られた粉末冶金用混合粉末を、下記のように成形した際に、その密度（単位：ｇ／ｃｍ3）および抜出し力（単位：ＭＰａ）を測定した。抜出し力の値が低いほど抜出し性に優れるものとして評価できる。
(Density and extraction force)
When the obtained powder mixture for powder metallurgy was molded as described below, its density (unit: g / cm 3 ) and extraction force (unit: MPa) were measured. The lower the extraction force value, the better the extraction performance.
（抗折強度）
圧粉体の抗折強度は、ドリル加工時に発生する割れに対する数値的指標である。
得られた粉末冶金用混合粉末について、日本粉末冶金工業会規格ＪＰＭＡ Ｐ１０−１９９２に準拠して、６９０ＭＰａの成形圧力で成形した圧粉体の抗折強度（単位：ＭＰａ）を求めた。抗折強度の値が大きいほど、圧粉体が高強度化されており、焼結前の圧粉体の加工性に優れるものとして評価できる。
(Folding strength)
The bending strength of the green compact is a numerical index for cracks that occur during drilling.
With respect to the obtained mixed powder for powder metallurgy, the bending strength (unit: MPa) of the green compact molded at a molding pressure of 690 MPa was determined in accordance with Japan Powder Metallurgy Industry Association Standard JPMA P10-1992. The larger the value of the bending strength, the higher the strength of the green compact, and it can be evaluated that it is excellent in the workability of the green compact before sintering.
なお、実施例５においては、圧粉体の抗折強度を求める前に、圧粉体に対して、１２０℃で３０分間の加熱硬化処理を行った。
実施例５以外の例では、抗折強度を求める前に圧粉体に対して加熱硬化処理を行わなかった。この場合、下記表１の加熱硬化処理条件の欄に「−」を記載した。
In Example 5, before obtaining the bending strength of the green compact, the green compact was subjected to a heat curing treatment at 120 ° C. for 30 minutes.
In examples other than Example 5, the green compact was not heat-cured before obtaining the bending strength. In this case, “-” is described in the column of the heat curing treatment conditions in Table 1 below.
上記表１に示す結果から明らかなように、まず、実施例１〜４と比較例１とを対比すると、液状硬化性化合物を内包するマイクロカプセルを配合した実施例１〜４の粉末冶金用混合粉末は、硬化性樹脂粉末を配合した比較例１の粉末冶金用混合粉末と比べて、流動度の値が小さく、流動性が良好であった。加えて、実施例１〜４は、比較例１よりも抗折強度の値が大きく、焼結前の圧粉体の加工性は、比較例１と同等以上に良好であることが示された。 As is clear from the results shown in Table 1 above, when Examples 1 to 4 are compared with Comparative Example 1, first, the powder metallurgy mixture of Examples 1 to 4 in which microcapsules encapsulating a liquid curable compound are blended. Compared with the mixed powder for powder metallurgy of Comparative Example 1 in which the curable resin powder was blended, the powder had a small fluidity value and good fluidity. In addition, Examples 1 to 4 had a higher bending strength value than Comparative Example 1, indicating that the processability of the green compact before sintering was equal to or better than Comparative Example 1. .
また、マイクロカプセルに内包されていない液状硬化性化合物を配合した比較例２は、上述した条件で流動度を求めようとしても、粉末冶金用混合粉末が流れず（容器から排出されず）、流動性が著しく劣ることが分かった。 Further, in Comparative Example 2 in which a liquid curable compound not encapsulated in microcapsules was blended, the powdered metallurgy mixed powder did not flow (not discharged from the container) and flowed even when the fluidity was obtained under the above-described conditions. It was found that the properties were extremely inferior.
また、実施例１〜４は、潤滑剤（ステアリン酸）を配合しなかったにもかかわらず、潤滑剤（ステアリン酸）を配合した標準例１と比べて、抜出し力の値はやや大きい程度であり、抜出し性が良好であった。これは、マイクロカプセルを含有することで、抜出し性が良好になったものと考えられる。 Moreover, although Examples 1-4 did not mix | blend a lubricant (stearic acid), compared with the standard example 1 which mix | blended the lubricant (stearic acid), the value of extraction force is a little large grade. There was good pull-out property. This is considered to be because the extractability is improved by containing the microcapsules.
なお、鉄基粉末１００質量部に対するマイクロカプセルの添加量が０．５質量部である実施例１、および、同添加量が０．７質量部である実施例２は、鉄基粉末のみである標準例２と比べて、流動度の値が小さく、流動性が良好であった。これは、マイクロカプセルを含有することで、流動性が良化したためと考えられる。 In addition, Example 1 in which the amount of microcapsules added to 100 parts by mass of iron-based powder is 0.5 parts by mass and Example 2 in which the added amount is 0.7 parts by mass are only iron-based powders. Compared with the standard example 2, the fluidity value was small and the fluidity was good. This is presumably because the fluidity was improved by containing microcapsules.
実施例５は、実施例１と同様に、流動度の値が小さく流動性が良好であり、かつ、抗折強度の値が大きく焼結前の圧粉体の加工性が良好であった。
実施例１と実施例５とを対比すると、圧粉体に対して加熱硬化処理を行わなかった実施例１よりも、圧粉体に対して加熱硬化処理を行った実施例５の方が、抗折強度の値がより大きかった。
As in Example 1, Example 5 had a small fluidity value and good fluidity, and had a large bending strength value and good workability of the green compact before sintering.
When Example 1 is compared with Example 5, Example 5 in which the heat-curing treatment was performed on the green compact was more effective than Example 1 in which the heat-curing treatment was not performed on the green compact. The value of the bending strength was larger.
Claims (2)
前記マイクロカプセル１が、液状硬化性化合物Ａを内包し、前記マイクロカプセル２が、前記液状硬化性化合物Ａとは異なる液状硬化性化合物Ｂを内包するか、または、前記マイクロカプセル１が、前記液状硬化性化合物Ａを内包し、前記マイクロカプセル２が、硬化剤および硬化促進剤からなる群から選ばれる少なくとも１種を内包し、
マイクロカプセルに内包されていない液状硬化性化合物の含有量が、前記鉄基粉末１００質量部に対して、０．１０質量部以下である、粉末冶金用混合粉末。 Containing iron-based powder, microcapsule 1, and microcapsule 2 different from microcapsule 1,
The microcapsule 1 contains the liquid curable compound A, and the microcapsule 2 contains the liquid curable compound B different from the liquid curable compound A, or the microcapsule 1 contains the liquid Encapsulating the curable compound A, the microcapsule 2 encapsulating at least one selected from the group consisting of 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 microcapsule is 0.10 parts by mass or less with respect to 100 parts by mass of the iron-based powder.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58126901A (en) * | 1982-01-21 | 1983-07-28 | 株式会社ウイテック ジャパン | Removal of binder from green body |
| JPH06183826A (en) * | 1991-06-01 | 1994-07-05 | Hoechst Ag | Molding material for production of inorganic sintering product |
| JP2000077221A (en) * | 1998-09-01 | 2000-03-14 | Sankyo Seiki Mfg Co Ltd | Granulated powder for rare earth magnet and manufacture of the same, and resin bonded magnet using the same and manufacture of the magnet |
| JP2004232079A (en) * | 2002-05-21 | 2004-08-19 | Jfe Steel Kk | Auxiliary material powder for powder metallurgy, iron based powdery mixture for powder metallurgy, and production method therefor |
| JP2006124777A (en) * | 2004-10-28 | 2006-05-18 | Kobe Steel Ltd | Powder mixture for powder metallurgy and green compact molding |
| WO2014103287A1 (en) * | 2012-12-28 | 2014-07-03 | Ｊｆｅスチール株式会社 | Iron-based powder for powder metallurgy |
| JP2014169394A (en) * | 2013-03-04 | 2014-09-18 | Asahi Kasei E-Materials Corp | Microcapsule type curing agent for epoxy resin |
-
2016
- 2016-10-04 JP JP2016196275A patent/JP6477650B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58126901A (en) * | 1982-01-21 | 1983-07-28 | 株式会社ウイテック ジャパン | Removal of binder from green body |
| JPH06183826A (en) * | 1991-06-01 | 1994-07-05 | Hoechst Ag | Molding material for production of inorganic sintering product |
| JP2000077221A (en) * | 1998-09-01 | 2000-03-14 | Sankyo Seiki Mfg Co Ltd | Granulated powder for rare earth magnet and manufacture of the same, and resin bonded magnet using the same and manufacture of the magnet |
| JP2004232079A (en) * | 2002-05-21 | 2004-08-19 | Jfe Steel Kk | Auxiliary material powder for powder metallurgy, iron based powdery mixture for powder metallurgy, and production method therefor |
| JP2006124777A (en) * | 2004-10-28 | 2006-05-18 | Kobe Steel Ltd | Powder mixture for powder metallurgy and green compact molding |
| WO2014103287A1 (en) * | 2012-12-28 | 2014-07-03 | Ｊｆｅスチール株式会社 | Iron-based powder for powder metallurgy |
| JP2014169394A (en) * | 2013-03-04 | 2014-09-18 | Asahi Kasei E-Materials Corp | Microcapsule type curing agent for epoxy resin |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |