JP7512243B2 - Paste composition, porous body and method for producing same - Google Patents
Paste composition, porous body and method for producing same Download PDFInfo
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- JP7512243B2 JP7512243B2 JP2021167654A JP2021167654A JP7512243B2 JP 7512243 B2 JP7512243 B2 JP 7512243B2 JP 2021167654 A JP2021167654 A JP 2021167654A JP 2021167654 A JP2021167654 A JP 2021167654A JP 7512243 B2 JP7512243 B2 JP 7512243B2
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- hollow glass
- porous body
- porosity
- glass particles
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Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Description
本発明は、多孔質体を形成するためのペースト組成物ならびにこの組成物を用いて得られた多孔質体およびその製造方法に関し、特に、ヒートパイプやベーパーチャンバーの筐体の内壁に付設され、作動液を毛細管力によって移動させて還流を行うウィック（多孔質体による毛細管状または網目状構造体）の形成に好適なペースト組成物ならびにこの組成物を用いて得られた多孔質体およびその製造方法に関する。 The present invention relates to a paste composition for forming a porous body, a porous body obtained using this composition, and a method for producing the same. In particular, the present invention relates to a paste composition suitable for forming a wick (a capillary or mesh-like structure made of a porous body) that is attached to the inner wall of the housing of a heat pipe or vapor chamber and moves and circulates a working fluid by capillary force, and a porous body obtained using this composition and a method for producing the same.
パソコンやモバイル端末などの情報端末機器には、半導体素子等の電子部品が搭載されているが、前記電子部品の冷却デバイスとしてヒートパイプが採用されている。また、端末機器の薄型化に対応して、薄型で効率のよい冷却デバイスとして、扁平したヒートパイプや、面型（平板型）のヒートパイプであるベーパーチャンバーが採用されている。近年では、素子の高集積化、高性能化により発熱量が増加し、また、端末機器の小型化が進むことで発熱密度が増加するため、より高度な放熱対策が重要になってきた。 Information terminal devices such as personal computers and mobile terminals are equipped with electronic components such as semiconductor elements, and heat pipes are used as cooling devices for these electronic components. In addition, in response to the trend toward thinner terminal devices, flat heat pipes and vapor chambers, which are surface-type (flat) heat pipes, are being used as thin and efficient cooling devices. In recent years, the amount of heat generated has increased due to the high integration and high performance of elements, and the heat density has increased due to the miniaturization of terminal devices, so more advanced heat dissipation measures have become important.
ヒートパイプ（またはベーパーチャンバー）は、水などの凝縮性の流体（作動流体）の潜熱を利用して効率的に熱の輸送を行う熱伝導素子である。ヒートパイプは、内部に作動流体を封入するための空間を有する密閉された筒状またはシート状の構造を有しており、筐体の外壁部は熱伝導率の良い金属（主に銅）で形成されている。筐体の内部には、作動流体が封入され、内壁面には毛細管力により作動流体を輸送するウィック（多孔質体による毛細管構造）が形成されている。 A heat pipe (or vapor chamber) is a heat transfer element that efficiently transports heat by utilizing the latent heat of a condensable fluid (working fluid) such as water. A heat pipe has a sealed cylindrical or sheet-like structure with a space inside to seal the working fluid, and the outer wall of the housing is made of a metal (mainly copper) with good thermal conductivity. The working fluid is sealed inside the housing, and a wick (capillary structure made of a porous material) that transports the working fluid by capillary force is formed on the inner wall surface.
このような構造を有するヒートパイプは、電子部品などの熱源と接触し、作動流体が気化する領域である蒸発部と、作動流体が凝縮して液化する領域である凝縮部とを備えており、作動流体を蒸発部と凝縮部との間で循環させることにより前記熱源で発生する熱を放熱している。詳しくは、蒸発部で蒸発した気相状態の作動流体が低温・低圧側の冷却部に移動することにより熱を輸送し、輸送先の凝縮部において作動流体を冷却して凝縮し、液相状態に戻った作動流体（作動液）をウィックの毛細管力によって、再び蒸発部（入熱部）に移動することにより、作動流体を還流させて循環させている。 A heat pipe with this structure has an evaporation section where the working fluid comes into contact with a heat source such as an electronic component and vaporizes, and a condensation section where the working fluid condenses and liquefies. The working fluid is circulated between the evaporation section and the condensation section to dissipate heat generated by the heat source. In more detail, the working fluid in a gaseous state that has evaporated in the evaporation section moves to the cooling section on the low-temperature, low-pressure side to transport heat, and in the condensation section to which it is transported, the working fluid is cooled and condensed, and the working fluid (working liquid) that has returned to a liquid state is moved again to the evaporation section (heat input section) by the capillary force of the wick, thereby refluxing and circulating the working fluid.
このようなウィックには、毛細管力を向上させるために、作動流体との濡れ性が良好であり、かつ液相状態の作動流体の液面に形成されるメニスカスでの実効毛細管半径が可及的に小さくなることが要求される。そこで、ウィックとしては、従来から、多孔質焼結体や極細線束などが利用されている。具体的には、金属メッシュ、金属極細線束、金属粉末（比較的粒径の大きい金属粒子）の焼結体、ガラスなどが提案されているが、ヒートパイプの性能は、ウィックの毛細管力と浸透性（作動流体の流れ易さ）に左右されるため、近年の端末機器の小型化・薄型化に対応した放熱対策として好適な新たなウィックが必要となっている。しかし、ウィックとして、金属メッシュや粒径の大きい金属粒子を用いる場合は薄型化に限界がある。 To improve the capillary force, such a wick is required to have good wettability with the working fluid and to have an effective capillary radius at the meniscus formed on the surface of the working fluid in the liquid phase as small as possible. For this reason, porous sintered bodies and ultra-fine wire bundles have traditionally been used as wicks. Specifically, metal mesh, ultra-fine metal wire bundles, sintered bodies of metal powder (metal particles with relatively large particle diameters), glass, etc. have been proposed, but since the performance of a heat pipe depends on the capillary force and permeability (ease of flow of the working fluid) of the wick, a new wick suitable as a heat dissipation measure that corresponds to the miniaturization and thinning of terminal devices in recent years is needed. However, there is a limit to how thin the wick can be made when metal mesh or metal particles with large particle diameters are used as the wick.
そこで、特開２００８－１２２０３０号公報（特許文献１）には、中心粒径（Ｄ５０）が５～５０μｍであり、主成分がデンドライト状（樹枝状）である電解銅粉粒子からなるヒートパイプ構成原料が開示されている。 JP 2008-122030 A (Patent Document 1) discloses a heat pipe raw material made of electrolytic copper powder particles with a median particle size (D50) of 5 to 50 μm and a dendritic (branch-like) main component.
特許文献１には、銅粉の形状が樹枝状であるために粒子の見掛密度が小さく、焼結後に空隙率の高い焼結体を得ることができるとされている。しかし、見掛密度の小さい電解銅粉を用いれば空隙率の高い焼結体は得られるものの、一つ一つの空隙サイズが小さいと作動流体の移動が不充分となるため、高い冷却能力を得ることが難しい。すなわち、見掛密度の小さい電解銅粉は粒子径サイズも小さいため樹枝構造の枝葉も細かく、それを焼結して得られる空隙も小さくなり易い。これに対して、枝葉を大きくして空隙サイズを大きくしようとすると、粒子径の大きな電解銅粉を用いることになり、見掛密度が大きくなる。そうすると、空隙率が小さくなったり、最大粒子径が大きすぎて薄型のウィックを製造するのが困難となる。すなわち、樹枝状の電解銅粉を用いても、薄型化と高空隙率とを両立できない。 Patent Document 1 states that the dendritic shape of the copper powder results in a low apparent density of the particles, and that a sintered body with a high porosity can be obtained after sintering. However, although a sintered body with a high porosity can be obtained by using electrolytic copper powder with a low apparent density, if the size of each void is small, the movement of the working fluid becomes insufficient, making it difficult to obtain high cooling capacity. In other words, electrolytic copper powder with a low apparent density has a small particle size, so the branches and leaves of the dendritic structure are fine, and the voids obtained by sintering it tend to be small. In contrast, if you try to increase the branches and leaves to increase the void size, you will have to use electrolytic copper powder with a large particle size, and the apparent density will increase. This will result in a small porosity or a maximum particle size that is too large, making it difficult to manufacture a thin wick. In other words, even if dendritic electrolytic copper powder is used, it is not possible to achieve both a thin wick and a high porosity.
従って、本発明の目的は、薄型（薄膜）で高空隙率であり、かつ内部に浸透する液体の移動性（浸透性および流れやすさ）に優れる多孔質体を形成できるペースト組成物ならびにこの組成物を用いて得られた多孔質体およびその製造方法を提供することにある。 The object of the present invention is therefore to provide a paste composition capable of forming a porous body that is thin (membrane) and highly porous, and has excellent mobility (permeability and flowability) for liquids that penetrate into the interior, as well as a porous body obtained using this composition and a method for producing the same.
本発明者等は、前記課題を達成するため鋭意検討した結果、中空ガラス粒子と金属粒子と有機ビヒクルとを組み合わせて調製したペーストを用いることにより、薄型（薄膜）で高空隙率であり、かつ内部に浸透する液体の移動性（浸透性および流れ易さ）に優れる多孔質体を形成できることを見出し、本発明を完成した。 As a result of intensive research into achieving the above object, the inventors discovered that by using a paste prepared by combining hollow glass particles, metal particles, and an organic vehicle, it is possible to form a porous body that is thin (membrane) and highly porous, and that has excellent mobility (permeability and flowability) for the liquid that penetrates into the interior, and thus completed the present invention.
すなわち、本発明のペースト組成物は、中空ガラス粒子、金属粒子および有機ビヒクルを含む。前記中空ガラス粒子と、前記金属粒子との体積比率が、前者：後者＝２０：８０～９７：３である。前記中空ガラス粒子の平均粒子径は２０～１５０μｍであり、見掛密度は０．５ｇ／ｃｍ３以下であってもよい。前記中空ガラス粒子は、ホウ珪酸ガラスまたはホウ珪酸ナトリウムガラスであってもよい。前記金属粒子はＣｕ単体粒子であってもよい。前記金属粒子の平均粒子径は０．０１～２０μｍであってもよい。前記ペースト組成物は、多孔質体を形成するための組成物であってもよい。前記多孔質体は、ヒートパイプまたはベーパーチャンバーのウィックであってもよい。 That is, the paste composition of the present invention includes hollow glass particles, metal particles, and an organic vehicle. The volume ratio of the hollow glass particles to the metal particles is 20:80 to 97:3. The hollow glass particles may have an average particle size of 20 to 150 μm and an apparent density of 0.5 g/cm 3 or less. The hollow glass particles may be borosilicate glass or sodium borosilicate glass. The metal particles may be Cu simplex particles. The metal particles may have an average particle size of 0.01 to 20 μm. The paste composition may be a composition for forming a porous body. The porous body may be a wick of a heat pipe or a vapor chamber.
本発明には、前記ペースト組成物を、前記中空ガラス粒子の軟化点以上の温度で焼成して多孔質体を製造する方法も含まれる。 The present invention also includes a method for producing a porous body by firing the paste composition at a temperature equal to or higher than the softening point of the hollow glass particles.
本発明には、金属およびガラスで形成され、かつ空隙率が６０～９５％である多孔質体も含まれる。 The present invention also includes porous bodies made of metal and glass and having a porosity of 60 to 95%.
本発明では、中空ガラス粒子と金属粒子と有機ビヒクルとを組み合わせて調製したペーストを用いるため、薄型（薄膜）で高空隙率であり、かつ内部に浸透する液体の移動性（浸透性および流れやすさ）に優れる多孔質体を製造できる。得られた多孔質体は、薄肉で高空隙率であるにも拘わらず、必要な膜強度を保持しており、中空ガラスの殻（シェル）を利用して空隙を形成するため、充分な空隙率が得られるとともに、空隙の割合を制御しやすく、吸水性の制御に優れる。また、薄膜化に対応して、粒径の小さい金属粒子を用いても、高空隙率の多孔質体を形成できる。さらに、ペースト状の形態であるため、中空ガラス粒子と金属粒子との分散性に優れるとともに、スクリーン印刷等の簡便な方法で自在に膜厚を制御できるため、生産性に優れる。そのため、近年の端末機器の小型化・薄型化に対応したヒートパイプまたはベーパーチャンバーにおいて、高度な放熱対策として好適な新たなウィックを形成できる。 In the present invention, a paste prepared by combining hollow glass particles, metal particles, and an organic vehicle is used, so that a porous body can be manufactured that is thin (thin film), has a high porosity, and has excellent mobility (permeability and flowability) of the liquid that penetrates inside. The obtained porous body has the necessary film strength despite being thin and having a high porosity, and since the voids are formed using the shell of the hollow glass, sufficient porosity can be obtained, and the proportion of voids can be easily controlled, and water absorption can be controlled with ease. In addition, a porous body with a high porosity can be formed even if metal particles with a small particle size are used in response to thinning. Furthermore, since it is in a paste form, the dispersion of the hollow glass particles and the metal particles is excellent, and the film thickness can be freely controlled by a simple method such as screen printing, so that it is highly productive. Therefore, a new wick suitable as an advanced heat dissipation measure can be formed in a heat pipe or vapor chamber that corresponds to the miniaturization and thinning of terminal devices in recent years.
［ペースト組成物］
本発明のペースト組成物は、中空ガラス粒子、金属粒子および有機ビヒクルを含む。本発明では、このペースト組成物を、前記中空ガラス粒子の軟化温度（軟化点）以上の温度で焼成することで、中空ガラス粒子の殻（シェル）であるガラスが溶融して中空ガラス粒子が互いに連結し、連続した空隙を形成する。この時、金属粒子同士も焼結し、空隙を多く含む金属多孔質体（金属を主要な構成要素とする複合多孔質体または金属多孔質体）を形成する。中空ガラス粒子を構成していて溶融したガラス成分は、多孔質体に残存するが、中空ガラス粒子の殻は薄いため、ガラス成分自体の実質的な体積は小さく、空隙の形成や熱伝導性を阻害しない。そのため、得られた複合多孔質体は、機能的には、金属多孔質体とみなすことができる。
[Paste composition]
The paste composition of the present invention includes hollow glass particles, metal particles, and an organic vehicle. In the present invention, the paste composition is fired at a temperature equal to or higher than the softening temperature (softening point) of the hollow glass particles, whereby the glass shell of the hollow glass particles melts and the hollow glass particles are connected to each other to form continuous voids. At this time, the metal particles are also sintered to form a metal porous body (a composite porous body or a metal porous body having metal as a main component) containing many voids. The molten glass component constituting the hollow glass particles remains in the porous body, but since the shell of the hollow glass particles is thin, the substantial volume of the glass component itself is small and does not inhibit the formation of voids or thermal conductivity. Therefore, the obtained composite porous body can be functionally regarded as a metal porous body.
さらに、本発明では、前記中空ガラス粒子の粒子径や添加量を変えることで、空隙率や空隙の大きさを容易に制御できる。そのため、ヒートパイプやベーパーチャンバーのウィックの構成材料として用いれば、ヒートパイプやベーパーチャンバーの筐体の内壁部に塗布して焼成することで、作動流体の吸収や移動性（浸透性）に適した空隙率や空隙サイズに容易に調整できる。さらには、空隙サイズを大きくするために粒子径の大きな中空ガラス粒子を選択した場合にも、焼成により中空ガラス粒子は流動するため、焼成膜（ウィック）の厚みが大きくなりすぎず、薄膜のウィックの形成にも好適に使用できる。 Furthermore, in the present invention, the porosity and pore size can be easily controlled by changing the particle size and amount of the hollow glass particles. Therefore, if it is used as a constituent material for the wick of a heat pipe or vapor chamber, it can be easily adjusted to a porosity and pore size suitable for the absorption and mobility (permeability) of the working fluid by applying it to the inner wall of the housing of the heat pipe or vapor chamber and firing it. Furthermore, even if hollow glass particles with a large particle size are selected to increase the pore size, the hollow glass particles flow upon firing, so the thickness of the fired film (wick) does not become too large, and it can also be suitably used for forming a thin wick.
（金属粒子）
金属粒子の金属種は特に制限されない。具体的には、金属としては、例えば、Ａｌ、Ｔｉ、Ｍｎ、Ｆｅ、Ｎｉ、Ｃｕ、Ｚｎ、Ｍｏ、Ｐｄ、Ａｇ、Ｗ、Ｐｔ、Ａｕなどが挙げられる。これらの金属は、単独でまたは二種以上組み合わせて使用できる。金属粒子は、異種の金属粒子の組み合わせであってもよく、二種以上を組み合わせた合金で形成されていてもよい。これらの金属の中で、ヒートパイプやベーパーチャンバー本体の外壁部が熱伝導性金属または合金、特に、Ｃｕで形成されることが多いことを考慮すれば、熱伝導性金属または合金粒子、特に、Ｃｕ単体粒子、Ｃｕの融点よりも低い温度で焼結が可能なＡｌやＡｕ、Ａｇなどの金属単体粒子、またはＡｇ－Ｐｄ、Ａｇ－Ｃｕ、Ａｇ－Ｐｔ、Ｃｕ－Ｎｉの混合もしくは合金粒子が好ましく、筐体の外壁部と同種であるうえに、性能（熱伝導性）、経済性などの観点で、Ｃｕ単体粒子が特に好ましい。
(Metal Particles)
The metal type of the metal particles is not particularly limited. Specifically, examples of metals include Al, Ti, Mn, Fe, Ni, Cu, Zn, Mo, Pd, Ag, W, Pt, and Au. These metals can be used alone or in combination of two or more. The metal particles may be a combination of different metal particles, or may be formed of an alloy combining two or more types. Among these metals, considering that the outer wall part of the heat pipe or vapor chamber body is often formed of a thermally conductive metal or alloy, especially Cu, thermally conductive metal or alloy particles, especially Cu single particles, metal single particles such as Al, Au, and Ag that can be sintered at a temperature lower than the melting point of Cu, or mixtures or alloy particles of Ag-Pd, Ag-Cu, Ag-Pt, and Cu-Ni are preferred, and Cu single particles are particularly preferred from the viewpoints of performance (thermal conductivity), economy, and the like, as well as being the same type as the outer wall part of the housing.
金属粒子（特にＣｕ単体粒子）の形状としては、例えば、球状（真球状または略球状）、楕円体（楕円球）状、多面体状（多角錘状、立方体状や直方体状など多角柱状など）、板状（扁平状、鱗片状、薄片状など）、ロッド状または棒状、繊維状、樹針状、樹枝状またはデンドライト状、多葉または星状（３～６葉状など）、ドッグボーン状、不定形状などが挙げられる。これらの形状のうち、通常、球状、楕円体状、多面体状、不定形状、樹枝状などであり、得られる多孔質体における液体の浸透性および流れ易さ（通液性）の点から、球状（真球状または略球状）、正多面体状（正六面体状または立方体状、正八面体状など）などの等方形状が好ましく、球状が特に好ましい。 Examples of shapes of metal particles (particularly Cu particles) include spherical (true or nearly spherical), ellipsoidal (elliptical sphere), polyhedral (polygonal pyramid, polygonal column such as cube or rectangular parallelepiped, etc.), plate-like (flat, scale, flake, etc.), rod or stick, fibrous, needle-like, dendritic or dendrite-like, multi-leaf or star-like (3-6 leaf-like, etc.), dog-bone, and irregular shapes. Among these shapes, the usual shapes are spherical, ellipsoidal, polyhedral, irregular, dendritic, etc., and from the viewpoint of the permeability and flowability (liquid permeability) of the liquid in the resulting porous body, isotropic shapes such as spherical (true or nearly spherical) and regular polyhedral (regular hexahedral, cubic, regular octahedral, etc.) are preferred, with spherical being particularly preferred.
なお、本願において、「球状」は、真球状および略球状の双方を含む意味で用いる。球状において、短径に対する長径の比は、例えば１～２、好ましくは１～１．５、さらに好ましくは１～１．３、より好ましくは１～１．２、最も好ましくは１～１．１である。また、等方形状は、略等方形状も含む。 In this application, the term "spherical" is used to include both a perfect sphere and an approximately spherical shape. In a sphere, the ratio of the major axis to the minor axis is, for example, 1 to 2, preferably 1 to 1.5, more preferably 1 to 1.3, even more preferably 1 to 1.2, and most preferably 1 to 1.1. In addition, an isotropic shape also includes an approximately isotropic shape.
金属粒子の平均粒子径は特に制限されない。中空ガラス粒子をできるだけ高充填にして、その隙間に金属粒子を存在させることで、多孔質体の高空隙率かつ高強度が担保される点から、金属粒子の平均粒子径（Ｄ５０）は、中空ガラス粒子の平均粒子径（Ｄ５０）よりも小さい方が好ましい。具体的に、金属粒子の平均粒子径は、例えば０．０１～１００μｍ、好ましくは０．５～６５μｍ、さらに好ましくは０．５～２０μｍ、より好ましくは１～１０μｍ、最も好ましくは３～８μｍである。また、金属粒子の平均粒子径（Ｄ５０）は、薄膜化と高空隙率とを両立できるとともに、軟化し易く、低温で焼成できる点から、２０μｍ以下であってもよく、例えば０．０１～２０μｍ、好ましくは０．１～１０μｍ、さらに好ましくは０．２～８μｍであってもよい。粒子径が小さすぎると、経済性が低下するとともに、組成物中での分散性も低下する虞があり、大きすぎると、多孔質性および吸水性が低下し、薄膜化が困難となる上に、中空ガラス粒子が多い際に金属粒子同士が離れて焼結できず構造が弱くなる虞がある。 The average particle diameter of the metal particles is not particularly limited. Since the hollow glass particles are filled as densely as possible and the metal particles are present in the gaps between the hollow glass particles, the average particle diameter (D50) of the metal particles is preferably smaller than the average particle diameter (D50) of the hollow glass particles, in order to ensure high porosity and high strength of the porous body. Specifically, the average particle diameter of the metal particles is, for example, 0.01 to 100 μm, preferably 0.5 to 65 μm, more preferably 0.5 to 20 μm, more preferably 1 to 10 μm, and most preferably 3 to 8 μm. In addition, the average particle diameter (D50) of the metal particles may be 20 μm or less, for example, 0.01 to 20 μm, preferably 0.1 to 10 μm, and more preferably 0.2 to 8 μm, in order to achieve both thinning and high porosity, as well as to be easily softened and sintered at a low temperature. If the particle size is too small, it may be less economical and may also reduce dispersibility in the composition; if it is too large, the porosity and water absorption properties may decrease, making it difficult to form a thin film, and when there are a lot of hollow glass particles, the metal particles may separate from each other and not be able to be sintered, weakening the structure.
金属粒子の９０体積％粒径（Ｄ９０）は１５０μｍ以下（例えば０．０２～１５０μｍ）であってもよく、例えば１００μｍ以下、好ましくは３０μｍ以下、さらに好ましくは１５μｍ以下、最も好ましくは１３μｍ以下（例えば５～１３μｍ）であってもよい。Ｄ９０が大きすぎると、得られる多孔質体の空隙率が低下する虞がある。 The 90 volume percent particle size (D90) of the metal particles may be 150 μm or less (e.g., 0.02 to 150 μm), for example, 100 μm or less, preferably 30 μm or less, more preferably 15 μm or less, and most preferably 13 μm or less (e.g., 5 to 13 μm). If D90 is too large, there is a risk that the porosity of the resulting porous body will decrease.
なお、本願において、粒子（金属粒子および後述する中空ガラス粒子）の平均粒子径および粒径分布は、レーザー回折散乱式粒度分布測定装置を用いて測定された中心粒径（Ｄ５０）および粒子径分布（体積基準）を意味する。 In this application, the average particle size and particle size distribution of particles (metal particles and hollow glass particles described later) refer to the median particle size (D50) and particle size distribution (volume basis) measured using a laser diffraction scattering type particle size distribution measuring device.
金属粒子の割合は、ペースト組成物中３０質量％以上であればよく、例えば３０～９０質量％、好ましくは４０～８０質量％、さらに好ましくは５０～７０質量％、より好ましくは５５～６５質量％である。金属粒子の割合が少なすぎると、得られる多孔質体において、金属間の結合が低下する虞がある。 The proportion of metal particles in the paste composition may be 30% by mass or more, for example, 30 to 90% by mass, preferably 40 to 80% by mass, more preferably 50 to 70% by mass, and even more preferably 55 to 65% by mass. If the proportion of metal particles is too low, there is a risk that the bonding between the metals in the resulting porous body will be reduced.
（中空ガラス粒子）
本発明における中空ガラス粒子は、中空ビーズまたはガラスバルーンとも称され、ガラス成分で形成され、粒子の外周を形成する殻（シェル）を有し、前記シェルの内部が空洞である構造を有している。中空ガラス粒子の内部の空洞は、多孔質体の空隙になるべき役割を担う。中空ガラス粒子の外周のシェルは、ペースト組成物中に溶媒が存在し、流動（変形）可能な状態であっても、ペースト組成物中で空洞を担保し、金属粒子同士の距離を離して金属粒子の過度な焼結を進みにくくして、空隙率を向上させる役割を担う。
(Hollow Glass Particles)
The hollow glass particles in the present invention are also called hollow beads or glass balloons, and are formed of glass components, have a shell that forms the outer periphery of the particle, and have a structure in which the inside of the shell is hollow. The internal cavities of the hollow glass particles serve to become the voids of the porous body. The shell on the outer periphery of the hollow glass particles plays a role in securing the voids in the paste composition even when a solvent is present in the paste composition and the particle is in a flowable (deformable) state, and in increasing the porosity by separating the metal particles from each other, making it difficult for the metal particles to be excessively sintered.
中空ガラス粒子のシェルを構成するガラス組成は、シェルが溶融して中空粒子が互いに連結して連続した空隙を形成できるものであれば特に限定されない。中空ガラス粒子を構成するガラス成分としては、例えば、ビスマス系ガラス、シリカ系ガラス、亜鉛系ガラス、ホウ珪酸系ガラス、ホウ珪酸亜鉛系ガラス、鉛系ガラスなどが挙げられる。 The glass composition constituting the shell of the hollow glass particles is not particularly limited as long as the shell can be melted and the hollow particles can be connected to each other to form continuous voids. Examples of glass components constituting the hollow glass particles include bismuth-based glass, silica-based glass, zinc-based glass, borosilicate glass, zinc borosilicate glass, and lead-based glass.
本発明では、前記ガラス成分の中から、シェルの軟化温度が焼成温度よりも低くなるように選定するのが好ましい。例えば、金属粒子がＣｕ単体粒子である場合、その焼成温度は６００～９００℃であることが多いため、シェルの軟化温度はその温度よりも低くなるよう選定する。例えば、ホウ珪酸ガラスの中空ガラス粒子（軟化点５５０℃）、ホウ珪酸ナトリウムガラス（軟化点４５０℃）の中空ガラス粒子が好ましい。具体的には、中空ガラス粒子を形成するガラス（シェル）の軟化点は、焼成温度よりも、１０℃以上低い軟化点であってもよく、５０～５００℃低い軟化点が好ましく、１００～４５０℃低い軟化点がさらに好ましく、２００～４００℃低い軟化点がより好ましく、３００～３５０℃低い軟化点が最も好ましい。具体的な軟化点は、例えば３００～６００℃、好ましくは４００～５５０℃であってもよい。 In the present invention, it is preferable to select from the glass components such that the softening temperature of the shell is lower than the firing temperature. For example, when the metal particles are Cu particles, the firing temperature is often 600 to 900°C, so the softening temperature of the shell is selected to be lower than that temperature. For example, hollow glass particles of borosilicate glass (softening point 550°C) and hollow glass particles of sodium borosilicate glass (softening point 450°C) are preferable. Specifically, the softening point of the glass (shell) forming the hollow glass particles may be a softening point 10°C or more lower than the firing temperature, preferably 50 to 500°C lower, more preferably 100 to 450°C lower, even more preferably 200 to 400°C lower, and most preferably 300 to 350°C lower. The specific softening point may be, for example, 300 to 600°C, preferably 400 to 550°C.
なお、本願において、ガラスの軟化点は、慣用の方法、例えば、熱重量示差熱分析装置（ＴＧ－ＤＴＡ）を用いて測定できる。 In this application, the softening point of glass can be measured by a conventional method, for example, using a thermogravimetric differential thermal analyzer (TG-DTA).
中空ガラス粒子の形状は特に制限されない。中空ガラス粒子の形状としては、例えば、前記金属粒子の形状として例示された形状から選択できる。前記形状のうち、得られる多孔質体の空隙の均一性を向上できる点から、等方形状が好ましく、球状が特に好ましい。 The shape of the hollow glass particles is not particularly limited. The shape of the hollow glass particles can be selected, for example, from the shapes exemplified as the shapes of the metal particles. Among the shapes, an isotropic shape is preferred, and a spherical shape is particularly preferred, in order to improve the uniformity of the voids in the resulting porous body.
中空ガラス粒子の平均粒子径（Ｄ５０）は、例えば１０～２００μｍ、好ましくは２０～１５０μｍ、さらに好ましくは４０～１００μｍ、より好ましくは６０～９０μｍである。さらに、中空ガラス粒子の平均粒子径（Ｄ５０）は、多孔質体の強度を向上できる点から、例えば１２～１５０μｍ、好ましくは１２～１００μｍ、さらに好ましくは１２～８０μｍ、より好ましくは１２～５０μｍ、最も好ましくは１２～３５μｍであってもよい。中空ガラス粒子の平均粒子径が小さすぎると、多孔質体の空隙サイズが小さくなると共に、中空ガラス粒子に占める空洞割合も小さくなるため、多孔質体の空隙率および吸水性が低くなる虞がある。平均粒子径が大きすぎる場合、多孔質体の空隙サイズが大きくなり、金属粒子同士の距離が遠くなって充分な焼結が得られず、金属間の結合構造が脆弱になるうえに、毛細管現象による作動流体の移動性（浸透性）および吸水性も低下する虞がある。 The average particle diameter (D50) of the hollow glass particles is, for example, 10 to 200 μm, preferably 20 to 150 μm, more preferably 40 to 100 μm, and more preferably 60 to 90 μm. Furthermore, the average particle diameter (D50) of the hollow glass particles may be, for example, 12 to 150 μm, preferably 12 to 100 μm, more preferably 12 to 80 μm, more preferably 12 to 50 μm, and most preferably 12 to 35 μm, in order to improve the strength of the porous body. If the average particle diameter of the hollow glass particles is too small, the pore size of the porous body will be small and the proportion of cavities in the hollow glass particles will also be small, which may result in a low porosity and water absorption of the porous body. If the average particle size is too large, the pore size of the porous body will be large, the distance between the metal particles will be too great, sufficient sintering will not be achieved, the bond structure between the metals will be weak, and there is a risk that the mobility (permeability) and water absorption of the working fluid due to capillary action will also decrease.
多孔質体の高空隙率かつ高強度を担保できる点から、中空ガラス粒子の平均粒子径（Ｄ５０）は、金属粒子の平均粒子径（Ｄ５０）よりも大きい方が好ましい。中空ガラス粒子の平均粒子径（Ｄ５０）は、金属粒子の平均粒子径（Ｄ５０）に対して１倍を超えていればよいが、１．１～３００倍程度の範囲から選択でき、例えば２～２５０倍、好ましくは３～２００倍、さらに好ましくは５～１００倍、より好ましくは１０～５０倍、最も好ましくは１５～２０倍である。 In order to ensure high porosity and high strength of the porous body, it is preferable that the average particle diameter (D50) of the hollow glass particles is larger than the average particle diameter (D50) of the metal particles. The average particle diameter (D50) of the hollow glass particles should be more than 1 time the average particle diameter (D50) of the metal particles, but can be selected from the range of about 1.1 to 300 times, for example 2 to 250 times, preferably 3 to 200 times, even more preferably 5 to 100 times, more preferably 10 to 50 times, and most preferably 15 to 20 times.
中空ガラス粒子の９０体積％粒径（Ｄ９０）は４００μｍ以下（例えば２０～４００μｍ）であってもよく、例えば３００μｍ以下、好ましくは２００μｍ以下、さらに好ましくは１８０μｍ以下（例えば１２０～１８０μｍ）であってもよい。Ｄ９０が大きすぎると、得られる多孔質体の空隙率が低下する虞がある。 The 90% volume particle size (D90) of the hollow glass particles may be 400 μm or less (e.g., 20 to 400 μm), for example, 300 μm or less, preferably 200 μm or less, and more preferably 180 μm or less (e.g., 120 to 180 μm). If D90 is too large, there is a risk that the porosity of the resulting porous body will decrease.
中空ガラス粒子は、前記粒径分布を有するのが好ましく、粒径分布は、ピークが１つである単峰性の分布であってもよく、ピークが２以上ある多峰性（例えば２峰性）の分布であってもよい。 The hollow glass particles preferably have the above particle size distribution, which may be a unimodal distribution with one peak, or a multimodal distribution with two or more peaks (e.g., bimodal).
中空ガラス粒子の見掛密度は、１．５ｇ／ｃｍ３以下であってもよく、例えば０．０５～１ｇ／ｃｍ３程度の範囲から選択できるが、空洞割合が大きく、空隙率を高め易い点から、０．５ｇ／ｃｍ３以下が好ましく、例えば０．０５～０．５ｇ／ｃｍ３、好ましくは０．０８～０．２ｇ／ｃｍ３、さらに好ましくは０．０９～０．１７ｇ／ｃｍ３、より好ましくは０．１～０．１６ｇ／ｃｍ３、最も好ましくは０．１２～０．１５ｇ／ｃｍ３である。見掛密度が小さすぎると、金属粒子同士の距離が遠くなって充分な焼結が得られず、金属間の結合構造が脆弱になる虞があり、大きすぎると、多孔質体の空隙率が低下する虞がある。 The apparent density of the hollow glass particles may be 1.5 g/cm3 or less , and can be selected from the range of, for example, about 0.05 to 1 g/cm3, but is preferably 0.5 g/cm3 or less, for example, 0.05 to 0.5 g/ cm3 , preferably 0.08 to 0.2 g/ cm3 , further preferably 0.09 to 0.17 g/ cm3 , more preferably 0.1 to 0.16 g/ cm3 , and most preferably 0.12 to 0.15 g/ cm3 , in view of the large hollow ratio and the ease of increasing the porosity. If the apparent density is too small, the distance between the metal particles becomes too far to obtain sufficient sintering, and there is a risk that the bond structure between the metals becomes weak, and if it is too large, there is a risk that the porosity of the porous body decreases.
なお、本願において、中空ガラス粒子の見掛密度は、中空部を粒子容積に含めた密度を意味し、慣用の方法で測定でき、例えば、ピクノメーター法などに基づいて測定できる。 In this application, the apparent density of hollow glass particles means the density including the hollow portion in the particle volume, and can be measured by a conventional method, for example, based on the pycnometer method.
中空ガラス粒子と金属粒子との体積比率は、多孔質体、特にウィック層に好適な空隙率を実現できる点から、２０：８０～９７：３であり、好ましくは６０：４０～９５：５、さらに好ましくは７０：３０～９３：７、より好ましくは８０：２０～９２：８、最も好ましくは８５：１５～９１：９である。さらに、中空ガラス粒子と金属粒子との体積比率は、多孔質体の強度を向上できる点から、好ましくは２０：８０～９５：５、さらに好ましくは２０：８０～９３：７、より好ましくは２０：８０～９０：１０であってもよい。金属粒子に対する中空ガラス粒子の体積比率が小さすぎると、多孔質体の空隙率が低くなり、毛細管現象による作動流体の移動性（浸透性）が低下する虞がある。一方、金属粒子に対する中空ガラス粒子の体積比率が大きすぎると、金属粒子が少ないため、金属粒子同士の距離が遠くなって充分な焼結が得られず、金属間の結合構造が脆弱になる虞がある。 The volume ratio of hollow glass particles to metal particles is 20:80 to 97:3, preferably 60:40 to 95:5, more preferably 70:30 to 93:7, more preferably 80:20 to 92:8, and most preferably 85:15 to 91:9, in order to achieve a suitable porosity for the porous body, particularly the wick layer. Furthermore, the volume ratio of hollow glass particles to metal particles may be preferably 20:80 to 95:5, more preferably 20:80 to 93:7, and more preferably 20:80 to 90:10, in order to improve the strength of the porous body. If the volume ratio of hollow glass particles to metal particles is too small, the porosity of the porous body will be low, and the mobility (permeability) of the working fluid due to capillary action may be reduced. On the other hand, if the volume ratio of hollow glass particles to metal particles is too high, there will be too few metal particles, so the distance between the metal particles will be too great and sufficient sintering will not be achieved, which may weaken the bond between the metal particles.
なお、本願において、中空ガラス粒子と金属粒子との体積比率は、原料の質量に対して、それぞれ見掛密度および比重から換算した値に基づいて算出できる。 In this application, the volume ratio of hollow glass particles to metal particles can be calculated based on the values converted from the apparent density and specific gravity, respectively, relative to the mass of the raw materials.
（有機ビヒクル）
有機ビヒクルは、ペースト組成物の有機ビヒクルとして利用される慣用の有機ビヒクル、例えば、有機バインダーおよび／または有機溶剤であってもよい。有機ビヒクルは、有機バインダーおよび有機溶剤のいずれか一方であってもよいが、通常、有機バインダーと有機溶剤との組み合わせ（有機バインダーの有機溶剤による溶解物）である。
(Organic Vehicle)
The organic vehicle may be a conventional organic vehicle used as an organic vehicle for a paste composition, such as an organic binder and/or an organic solvent. The organic vehicle may be either an organic binder or an organic solvent, but is usually a combination of an organic binder and an organic solvent (a solution of the organic binder in the organic solvent).
有機バインダーとしては、特に限定されず、例えば、熱可塑性樹脂（オレフィン系樹脂、ビニル系樹脂、アクリル系樹脂、スチレン系樹脂、ポリエーテル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、セルロース誘導体など）、熱硬化性樹脂（熱硬化性アクリル系樹脂、エポキシ樹脂、フェノール樹脂、不飽和ポリエステル系樹脂、ポリウレタン系樹脂など）、ゴム類（ポリブタジエン、ポリイソプレンなど）などが挙げられる。これらの有機バインダーは、単独でまたは二種以上組み合わせて使用できる。これらの有機バインダーのうち、焼成過程で容易に焼失し、かつ灰分の少ない樹脂、例えば、アクリル系樹脂（ポリメチルメタクリレート、ポリブチルメタクリレートなど）、セルロース誘導体（ニトロセルロース、エチルセルロース、ブチルセルロース、酢酸セルロースなど）、ポリエーテル類（ポリオキシメチレンなど）などが汎用され、熱分解性などの点から、ポリ（メタ）アクリル酸メチルやポリ（メタ）アクリル酸ブチルなどのポリ（メタ）アクリル酸Ｃ１－１０アルキルエステルやエチルセルロースが好ましい。 The organic binder is not particularly limited, and examples thereof include thermoplastic resins (olefin resins, vinyl resins, acrylic resins, styrene resins, polyether resins, polyester resins, polyamide resins, cellulose derivatives, etc.), thermosetting resins (thermosetting acrylic resins, epoxy resins, phenol resins, unsaturated polyester resins, polyurethane resins, etc.), and rubbers (polybutadiene, polyisoprene, etc.). These organic binders can be used alone or in combination of two or more. Among these organic binders, resins that are easily burned off during the firing process and have low ash content, such as acrylic resins (polymethyl methacrylate, polybutyl methacrylate, etc.), cellulose derivatives (nitrocellulose, ethyl cellulose, butyl cellulose, cellulose acetate, etc.), and polyethers (polyoxymethylene, etc.), are widely used, and from the viewpoint of thermal decomposition, poly(meth)acrylic acid C 1-10 alkyl esters such as poly(methyl meth)acrylate and poly(butyl meth)acrylate, and ethyl cellulose are preferred.
有機溶剤としては、特に限定されず、ペースト組成物に適度な粘性を付与し、かつペースト組成物を基材に塗布した後に乾燥処理によって容易に揮発できる有機化合物であればよく、高沸点の有機溶剤であってもよい。このような有機溶剤としては、例えば、芳香族炭化水素（パラキシレンなど）、エステル類（乳酸エチルなど）、ケトン類（イソホロンなど）、アミド類（ジメチルホルムアミドなど）、脂肪族アルコール（オクタノール、デカノール、ジアセトンアルコールなど）、セロソルブ類（メチルセロソルブ、エチルセロソルブなど）、セロソルブアセテート類（エチルセロソルブアセテート、ブチルセロソルブアセテートなど）、カルビトール類（カルビトール、メチルカルビトール、エチルカルビトールなど）、カルビトールアセテート類（エチルカルビトールアセテート、ブチルカルビトールアセテート）、脂肪族多価アルコール類（エチレングリコール、ジエチレングリコール、ジプロピレングリコール、ブタンジオール、トリエチレングリコール、グリセリンなど）、脂環族アルコール類［例えば、シクロヘキサノールなどのシクロアルカノール類；テルピネオール、ジヒドロテルピネオールなどのテルペンアルコール類（モノテルペンアルコールなど）など］、芳香族アルコール類（メタクレゾールなど）、芳香族カルボン酸エステル類（ジブチルフタレート、ジオクチルフタレートなど）、窒素含有複素環化合物（ジメチルイミダゾール、ジメチルイミダゾリジノンなど）などが挙げられる。これらの有機溶剤は、単独でまたは二種以上組み合わせて使用できる。これらの有機溶剤のうち、ペーストの流動性などの点から、テルピネオールなどの脂環族アルコール、ブチルカルビトールアセテートなどのＣ１－４アルキルセロソルブアセテート類が好ましい。 The organic solvent is not particularly limited, and may be an organic compound that imparts an appropriate viscosity to the paste composition and can be easily volatilized by drying after the paste composition is applied to a substrate, and may be a high-boiling organic solvent. Examples of such organic solvents include aromatic hydrocarbons (e.g., paraxylene), esters (e.g., ethyl lactate), ketones (e.g., isophorone), amides (e.g., dimethylformamide), aliphatic alcohols (e.g., octanol, decanol, diacetone alcohol), cellosolves (e.g., methyl cellosolve, ethyl cellosolve), cellosolve acetates (e.g., ethyl cellosolve acetate, butyl cellosolve acetate), carbitols (e.g., carbitol, methyl carbitol, ethyl carbitol), carbitol acetates (e.g., ethyl carbitol acetate, butyl carbitol acetate), and the like. Examples of the organic solvent include aliphatic polyhydric alcohols (ethylene glycol, diethylene glycol, dipropylene glycol, butanediol, triethylene glycol, glycerin, etc.), alicyclic alcohols [for example, cycloalkanols such as cyclohexanol; terpene alcohols (monoterpene alcohols, etc.) such as terpineol and dihydroterpineol], aromatic alcohols (metacresol, etc.), aromatic carboxylic acid esters (dibutyl phthalate, dioctyl phthalate, etc.), and nitrogen-containing heterocyclic compounds (dimethylimidazole, dimethylimidazolidinone, etc.). These organic solvents can be used alone or in combination of two or more. Among these organic solvents, alicyclic alcohols such as terpineol and C 1-4 alkyl cellosolve acetates such as butyl carbitol acetate are preferred from the viewpoint of the fluidity of the paste.
有機バインダーと有機溶剤とを組み合わせる場合、有機バインダーの割合は、有機溶剤１００質量部に対して、例えば１～２００質量部、好ましくは１０～１００質量部、さらに好ましくは３０～８０質量部程度であり、有機ビヒクル全体に対して１～８０質量％、好ましくは５～５０質量％、さらに好ましくは１０～４０質量％程度である。 When an organic binder is combined with an organic solvent, the ratio of the organic binder is, for example, 1 to 200 parts by mass, preferably 10 to 100 parts by mass, and more preferably about 30 to 80 parts by mass, relative to 100 parts by mass of the organic solvent, and is 1 to 80% by mass, preferably 5 to 50% by mass, and more preferably about 10 to 40% by mass relative to the total organic vehicle.
有機ビヒクルの質量割合は、ペースト組成物中５～８０質量％、好ましくは１０～７５質量％、さらに好ましくは２０～７０質量％である。有機ビヒクルの割合が少なすぎると、取り扱い性が低下する虞があり、多すぎると、金属間の結合構造が脆弱になる虞がある。 The mass ratio of the organic vehicle in the paste composition is 5 to 80 mass%, preferably 10 to 75 mass%, and more preferably 20 to 70 mass%. If the proportion of the organic vehicle is too low, there is a risk that the handling properties will decrease, and if the proportion is too high, there is a risk that the bond structure between the metals will become weak.
（他の成分）
ペースト組成物は、本発明の効果を損なわない範囲で、慣用の添加剤をさらに含んでいてもよい。慣用の添加剤としては、例えば、無機バインダー（中実のガラスフリットなど）、硬化剤（アクリル系樹脂の硬化剤など）、分解促進剤（金属酸化物など）、着色剤（染顔料など）、色相改良剤、染料定着剤、光沢付与剤、金属腐食防止剤、安定剤（酸化防止剤、紫外線吸収剤など）、界面活性剤又は分散剤（アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤、両性界面活性剤など）、分散安定化剤、粘度調整剤又はレオロジー調整剤、保湿剤、チクソトロピー性賦与剤、レベリング剤、消泡剤、殺菌剤、充填剤などが挙げられる。これらの他の成分は、単独でまたは二種以上組み合わせて使用できる。他の成分の割合は、成分の種類に応じて選択でき、通常、ペースト組成物全体に対して１０質量％以下（例えば０．０１～１０質量％）程度である。
(Other ingredients)
The paste composition may further contain conventional additives within a range that does not impair the effects of the present invention. Examples of conventional additives include inorganic binders (solid glass frit, etc.), hardeners (acrylic resin hardeners, etc.), decomposition accelerators (metal oxides, etc.), colorants (dye pigments, etc.), hue improvers, dye fixing agents, gloss imparting agents, metal corrosion inhibitors, stabilizers (antioxidants, ultraviolet absorbers, etc.), surfactants or dispersants (anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc.), dispersion stabilizers, viscosity adjusters or rheology adjusters, moisturizers, thixotropic agents, leveling agents, defoamers, bactericides, fillers, etc. These other components can be used alone or in combination of two or more. The proportion of the other components can be selected depending on the type of component, and is usually about 10% by mass or less (for example, 0.01 to 10% by mass) relative to the entire paste composition.
［多孔質体およびその製造方法］
本発明の多孔質体は、前記ペースト組成物を焼成することにより製造でき、例えば、前記ペースト組成物を基材の上に塗布して塗膜を形成する塗布工程と、前記塗膜を焼成して多孔質を得る焼成工程を含む製造方法により製造できる。
[Porous body and method for producing same]
The porous body of the present invention can be produced by firing the paste composition, for example, by a production method including a coating step of applying the paste composition onto a substrate to form a coating film, and a firing step of firing the coating film to obtain a porous body.
塗布工程において、ペースト組成物を基材に塗布して塗膜を形成する方法としては、例えば、スクリーン印刷法、インクジェット印刷法、凹版印刷法（例えば、グラビア印刷法など）、平版印刷法、オフセット印刷法、フレキソ印刷法などの印刷法やこれらの印刷法を組み合わせた印刷法、スピンコート法、ディップ法、ロール圧入法、スギージ圧入法、プレス圧入法などの直接圧入法などが挙げられる。これらの方法のうち、スクリーン印刷法が好ましい。 In the coating step, examples of the method for forming a coating film by coating the paste composition on a substrate include screen printing, inkjet printing, intaglio printing (e.g., gravure printing), lithographic printing, offset printing, flexographic printing, and other printing methods, as well as combinations of these printing methods, spin coating, dipping, and direct pressing methods such as roll pressing, sugege pressing, and press pressing. Of these methods, screen printing is preferred.
塗膜として基材に付着させたペースト組成物は、焼成処理の前に、自然乾燥してもよいが、加熱して乾燥してもよい。加熱温度は、有機溶媒の種類に応じて選択でき、例えば５０～２００℃、好ましくは８０～１８０℃、さらに好ましくは１００～１５０℃である。加熱時間は、例えば１分～３時間、好ましくは５分～２時間、さらに好ましくは１０分～１時間である。 The paste composition applied to the substrate as a coating film may be naturally dried or may be dried by heating before the firing treatment. The heating temperature can be selected according to the type of organic solvent, and is, for example, 50 to 200°C, preferably 80 to 180°C, and more preferably 100 to 150°C. The heating time is, for example, 1 minute to 3 hours, preferably 5 minutes to 2 hours, and more preferably 10 minutes to 1 hour.
基材の材質としては、多孔質体の種類に応じて選択でき、前記金属粒子の項で例示された金属から選択できる。多孔質体をヒートパイプやベーパーチャンバーのウィックとして利用する場合、基材はヒートパイプやベーパーチャンバーの筐体であり、前記筐体は、熱伝導性金属または合金、例えば、Ｃｕで形成されている場合が多い。 The material of the substrate can be selected according to the type of porous body, and can be selected from the metals exemplified in the section on metal particles above. When the porous body is used as a wick for a heat pipe or vapor chamber, the substrate is the housing of the heat pipe or vapor chamber, and the housing is often made of a thermally conductive metal or alloy, for example, Cu.
焼成工程において、焼成温度は、金属ペースト組成物中の中空ガラス粒子のシェルが軟化し、かつ金属粒子が焼結する温度以上であればよい。焼成温度は、金属粒子の種類に応じて選択できるが、中空ガラス粒子の軟化点以上であってもよく、前記軟化点よりも、１０℃以上高い温度が好ましく、５０～５００℃高い温度がさらに好ましく、１００～４５０℃高い温度が特に好ましく、２００～４００℃高い温度がより好ましく、３００～３５０℃高い温度が最も好ましい。 In the firing step, the firing temperature may be equal to or higher than the temperature at which the shells of the hollow glass particles in the metal paste composition soften and the metal particles sinter. The firing temperature can be selected according to the type of metal particles, but may be equal to or higher than the softening point of the hollow glass particles. A temperature 10°C or higher than the softening point is preferable, a temperature 50 to 500°C higher is more preferable, a temperature 100 to 450°C higher is particularly preferable, a temperature 200 to 400°C higher is more preferable, and a temperature 300 to 350°C higher is most preferable.
具体的な焼成温度（最高到達温度）は４５０℃以上であってもよく、例えば５５０～１０００℃、好ましくは６５０～９５０℃、さらに好ましくは７００～９００℃である。 Specific firing temperatures (maximum temperature reached) may be 450°C or higher, for example 550 to 1000°C, preferably 650 to 950°C, and more preferably 700 to 900°C.
焼成温度が低すぎると、中空ガラス粒子のシェルが溶けずに連結した空隙が形成されなかったり、金属粒子同士が焼結できなかったりする虞がある。一方、焼成温度が高すぎると、金属粒子の焼結が進みすぎて中空ガラス粒子の空洞（金属多孔質体の空隙）が塞がれたり、基材（ヒートパイプやベーパーチャンバーの筐体の外壁部）である銅板が溶出する虞がある。 If the firing temperature is too low, there is a risk that the shells of the hollow glass particles will not melt and connected voids will not be formed, or that the metal particles will not be able to sinter together. On the other hand, if the firing temperature is too high, there is a risk that the metal particles will sinter too much, blocking the cavities in the hollow glass particles (voids in the metal porous body) or dissolving the copper plate that is the base material (the outer wall of the housing of the heat pipe or vapor chamber).
焼成時間（最高到達温度での焼成時間）は、例えば１分～３時間、好ましくは３分～１時間、さらに好ましくは５～３０分である。 The firing time (firing time at the maximum temperature reached) is, for example, 1 minute to 3 hours, preferably 3 minutes to 1 hour, and more preferably 5 to 30 minutes.
なお、焼成の雰囲気は、金属粒子の種類に応じて選択でき、特に限定されず、空気中、不活性ガス（例えば、窒素ガス、アルゴンガス、ヘリウムガスなど）雰囲気中、真空雰囲気中のいずれかであってもよい。基材がＣｕで形成されている場合は、酸化を防ぐために不活性ガス雰囲気中が好ましく、経済性の面から、窒素雰囲気中が特に好ましい。 The sintering atmosphere can be selected according to the type of metal particles, and is not particularly limited, and may be in air, in an inert gas (e.g., nitrogen gas, argon gas, helium gas, etc.) atmosphere, or in a vacuum atmosphere. When the substrate is made of Cu, an inert gas atmosphere is preferred to prevent oxidation, and a nitrogen atmosphere is particularly preferred from an economical standpoint.
焼成（特に窒素雰囲気中での焼成）は、バッチ炉またはベルト搬送式のトンネル炉を用いて行ってもよい。 Firing (especially in a nitrogen atmosphere) may be carried out using a batch furnace or a belt-conveying tunnel furnace.
焼成により形成された焼成膜は、多孔質体を形成している。得られた多孔質体の表面または内部は、物理的な処理または化学的な処理に供してもよい。物理的な処理方法としては、例えば、表面を揃えるための研磨処理があり、バフ研磨、ラップ研磨、ポリッシング研磨などが挙げられる。化学的な処理方法としては、例えば、過硫酸ナトリウム水溶液などで最表面をソフトエッチングする方法や電解めっき処理・無電解めっき処理などが挙げられる。また、作動流体の吸収性や移動性を高める目的でプラズマ親水化処理や各種親水性コーティングなどを施してもよい。 The fired film formed by firing forms a porous body. The surface or interior of the resulting porous body may be subjected to physical or chemical treatment. Physical treatment methods include, for example, polishing to make the surface uniform, such as buffing, lapping, and polishing. Chemical treatment methods include, for example, soft etching of the outermost surface with an aqueous sodium persulfate solution, electrolytic plating, and electroless plating. In addition, plasma hydrophilization treatment and various hydrophilic coatings may be applied to increase the absorbency and mobility of the working fluid.
本発明の多孔質体は、金属およびガラスで形成され、高空隙率である。本発明の多孔質体の空隙率は、５０～９８％程度の範囲から選択でき、例えば６０～９５％、好ましくは７０～９３％、さらに好ましくは７５～９２％、より好ましくは８０～９０％、最も好ましくは８５～８８％である。空隙率が小さすぎると、通液性が低下する虞があり、高すぎると、強度低下する虞がある。 The porous body of the present invention is formed of metal and glass and has a high porosity. The porosity of the porous body of the present invention can be selected from a range of about 50 to 98%, for example, 60 to 95%, preferably 70 to 93%, further preferably 75 to 92%, more preferably 80 to 90%, and most preferably 85 to 88%. If the porosity is too small, there is a risk of reduced liquid permeability, and if it is too high, there is a risk of reduced strength.
なお、本願において、多孔質体の空隙率は、後述する実施例に記載の方法で測定できる。 In this application, the porosity of the porous body can be measured by the method described in the examples below.
本発明の多孔質体は、薄肉に形成でき、平均厚みは、例えば１０～３００μｍ、好ましくは３０～２００μｍ、さらに好ましくは５０～１５０μｍ、より好ましくは８０～１２０μｍ、最も好ましくは９０～１１０μｍである。 The porous body of the present invention can be formed to be thin, with an average thickness of, for example, 10 to 300 μm, preferably 30 to 200 μm, more preferably 50 to 150 μm, even more preferably 80 to 120 μm, and most preferably 90 to 110 μm.
なお、本願において、多孔質体の平均厚みは、後述する実施例に記載の方法で測定できる。 In this application, the average thickness of the porous body can be measured by the method described in the examples below.
本発明の多孔質体は、作動流体の浸透性や移動性に優れている。本発明の多孔質体の吸水性は、多孔質体の３０ｍｍの長さを吸い上げる速度で評価でき、４０秒以下であってもよく、好ましくは３０秒以下、さらに好ましくは２０秒以下、より好ましくは１０秒以下である。 The porous body of the present invention has excellent permeability and mobility of the working fluid. The water absorption of the porous body of the present invention can be evaluated by the speed at which the porous body absorbs a length of 30 mm, and may be 40 seconds or less, preferably 30 seconds or less, more preferably 20 seconds or less, and even more preferably 10 seconds or less.
なお、本願において、吸水性は、後述する実施例に記載の方法で測定できる。 In this application, water absorbency can be measured by the method described in the Examples below.
作動流体としては、例えば、水、メタノール、エタノール、アンモニア、フロンなどが挙げられる。これらのうち、ヒートパイプやベーパーチャンバーの作動流体としては水が好ましい。 Examples of working fluids include water, methanol, ethanol, ammonia, and freon. Of these, water is preferred as the working fluid for heat pipes and vapor chambers.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。以下の例において、実施例で使用した材料、ペースト組成物の調製方法および評価試料の作製方法、得られた評価試料の評価方法を以下に示す。 The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. In the following examples, the materials used in the examples, the method for preparing the paste composition and the method for producing the evaluation samples, and the method for evaluating the obtained evaluation samples are shown below.
［使用した材料］
（金属粒子）
Ｃｕ粒子１…球状、平均粒子径Ｄ５０：０．２μｍ、Ｄ９０：０．３μｍ、比重８．９
Ｃｕ粒子２…球状、平均粒子径Ｄ５０：０．５μｍ、Ｄ９０：０．８μｍ、比重８．９
Ｃｕ粒子３…球状、平均粒子径Ｄ５０：５μｍ、Ｄ９０：８μｍ、比重８．９
Ｃｕ粒子４…球状、平均粒子径Ｄ５０：６５μｍ、Ｄ９０：１１８μｍ、比重８．９
Ｃｕ粒子５…樹枝状、電解銅粉、平均粒子径Ｄ５０：２０μｍ、Ｄ９０：４０μｍ、見掛密度：０．８ｇ／ｃｍ３
Ｃｕ粒子６…樹枝状、電解銅粉、平均粒子径Ｄ５０：８５μｍ、Ｄ９０：１４０μｍ、見掛密度：２．１ｇ／ｃｍ３
Ａｇ粒子…球状、平均粒子径Ｄ５０：１μｍ、Ｄ９０：１．７μｍ、比重１０．５。
[Materials used]
(Metal Particles)
Cu particle 1...spherical, average particle size D50: 0.2 μm, D90: 0.3 μm, specific gravity 8.9
Cu particles 2...spherical, average particle size D50: 0.5 μm, D90: 0.8 μm, specific gravity 8.9
Cu particles 3...spherical, average particle size D50: 5 μm, D90: 8 μm, specific gravity 8.9
Cu particles 4...spherical, average particle size D50: 65 μm, D90: 118 μm, specific gravity 8.9
Cu particles 5...dendritic, electrolytic copper powder, average particle diameter D50: 20 μm, D90: 40 μm, apparent density: 0.8 g/cm 3
Cu particles 6...dendritic, electrolytic copper powder, average particle diameter D50: 85 μm, D90: 140 μm, apparent density: 2.1 g/cm 3
Ag particles: spherical, average particle size D50: 1 μm, D90: 1.7 μm, specific gravity 10.5.
（中空ガラス粒子）
中空ガラス粒子１…ホウ珪酸ナトリウムガラス、球状、平均粒子径Ｄ５０：８０μｍ、Ｄ９０：１５０μｍ、見掛密度：０．１４ｇ／ｃｍ３、耐熱温度（中空形状の維持に関係する耐熱温度であり、厳密には軟化点とは異なる温度）４５０℃
中空ガラス粒子２…ホウ珪酸ガラス、球状、平均粒子径Ｄ５０：１２μｍ、Ｄ９０：２０μｍ、見掛密度１．１０ｇ／ｃｍ３、耐熱温度５５０℃
中空ガラス粒子３…ホウ珪酸ナトリウムガラス、球状、平均粒子径Ｄ５０：２０μｍ、Ｄ９０：３５μｍ、見掛密度：０．４６ｇ／ｃｍ３、耐熱温度４５０℃
中空ガラス粒子４…ホウ珪酸ガラス、球状、平均粒子径Ｄ５０：３５μｍ、Ｄ９０：４５μｍ、見掛密度：０．３４ｇ／ｃｍ３、耐熱温度５５０℃
中空ガラス粒子５：ホウ珪酸ナトリウムガラス、球状、平均粒子径Ｄ５０：４０μｍ、Ｄ９０：８０μｍ、見掛密度：０．２０ｇ／ｃｍ３、耐熱温度４５０℃
中空ガラス粒子６：ホウ珪酸ナトリウムガラス、球状、平均粒子径Ｄ５０：６０μｍ、Ｄ９０：１０５μｍ、見掛密度：０．１８ｇ／ｃｍ３、耐熱温度４５０℃
中空ガラス粒子７：ホウ珪酸ナトリウムガラス、球状、平均粒子径Ｄ５０：１００μｍ、Ｄ９０：１７０μｍ、見掛密度：０．１１ｇ／ｃｍ３、耐熱温度４５０℃
中空ガラス粒子８：ホウ珪酸ナトリウムガラス、球状、平均粒子径Ｄ５０：１２０μｍ、Ｄ９０：１８５μｍ、見掛密度：０．１０ｇ／ｃｍ３、耐熱温度４５０℃
中空ガラス粒子９：ホウ珪酸ナトリウムガラス、球状、平均粒子径Ｄ５０：１５０μｍ、Ｄ９０：２２０μｍ、見掛密度：０．０８ｇ／ｃｍ３、耐熱温度４５０℃
中空ガラス粒子１０：ホウ珪酸ナトリウムガラス、球状、平均粒子径Ｄ５０：１８０μｍ、Ｄ９０：２５５μｍ、見掛密度：０．０７ｇ／ｃｍ３、耐熱温度４５０℃
(Hollow Glass Particles)
Hollow glass particles 1...sodium borosilicate glass, spherical, average particle size D50: 80 μm, D90: 150 μm, apparent density: 0.14 g/cm 3 , heat-resistant temperature (heat-resistant temperature related to maintaining the hollow shape, strictly speaking different from the softening point) 450° C.
Hollow glass particles 2...borosilicate glass, spherical, average particle size D50: 12 μm, D90: 20 μm, apparent density 1.10 g/cm 3 , heat-resistant temperature 550° C.
Hollow glass particles 3...sodium borosilicate glass, spherical, average particle size D50: 20 μm, D90: 35 μm, apparent density: 0.46 g/cm 3 , heat-resistant temperature: 450° C.
Hollow glass particles 4...borosilicate glass, spherical, average particle size D50: 35 μm, D90: 45 μm, apparent density: 0.34 g/cm 3 , heat-resistant temperature: 550° C.
Hollow glass particles 5: sodium borosilicate glass, spherical, average particle size D50: 40 μm, D90: 80 μm, apparent density: 0.20 g/cm 3 , heat-resistant temperature 450° C.
Hollow glass particles 6: sodium borosilicate glass, spherical, average particle size D50: 60 μm, D90: 105 μm, apparent density: 0.18 g/cm 3 , heat-resistant temperature 450° C.
Hollow glass particles 7: sodium borosilicate glass, spherical, average particle size D50: 100 μm, D90: 170 μm, apparent density: 0.11 g/cm 3 , heat-resistant temperature 450° C.
Hollow glass particles 8: sodium borosilicate glass, spherical, average particle size D50: 120 μm, D90: 185 μm, apparent density: 0.10 g/cm 3 , heat-resistant temperature 450° C.
Hollow glass particles 9: sodium borosilicate glass, spherical, average particle size D50: 150 μm, D90: 220 μm, apparent density: 0.08 g/cm 3 , heat-resistant temperature 450° C.
Hollow glass particles 10: sodium borosilicate glass, spherical, average particle size D50: 180 μm, D90: 255 μm, apparent density: 0.07 g/cm 3 , heat-resistant temperature 450° C.
（有機ビヒクル）
有機バインダーであるアクリル樹脂と、有機溶剤であるテレピネオールとを、有機バインダー：有機溶剤＝１：４の質量比で混合した混合物。
(Organic Vehicle)
A mixture of an acrylic resin as an organic binder and terpineol as an organic solvent in a mass ratio of organic binder:organic solvent=1:4.
［ペースト組成物の調製］
表１～４に示す組成で各原料を秤量し、遊星式脱泡撹拌機にて十分に混合することによって、ペースト組成物を調製した。
[Preparation of Paste Composition]
Each raw material was weighed out according to the composition shown in Tables 1 to 4, and thoroughly mixed with a planetary degassing mixer to prepare a paste composition.
［評価試料の作製］
無酸素銅板（６０ｍｍ×６０ｍｍ×０．２ｍｍ厚み）の表面にメタルマスクを用いて縦５０ｍｍ×横１５ｍｍのパターンをスクリーン印刷法で塗布して塗膜を形成した。メタルマスクの厚さは、中空ガラス粒子の平均粒子径に応じて使い分け、中空ガラス粒子の平均粒子径Ｄ５０が１５０μｍ以下の場合は、厚さ０．１２ｍｍのメタルマスクを用い、中空ガラス粒子の平均粒子径Ｄ５０が１５０μｍ以上の場合は、厚さ０．３０ｍｍのメタルマスクを用いた。１２０℃の送風乾燥機で１０分間、塗膜を乾燥させた後、焼成して焼成膜を形成した。なお、焼成条件としては、金属粒子としてＣｕ粒子を用いた場合は、ベルト式連続焼成炉にて窒素雰囲気中、温度８００℃、ピーク保持時間１０分間焼成した。排出するまでの総時間は６０分であった。金属粒子としてＡｇ粒子を用いた場合は、ベルト式連続焼成炉にて大気雰囲気中、温度６００℃であること以外は、Ｃｕ粒子を用いた場合と同様に焼成した。
[Preparation of evaluation samples]
A metal mask was used to apply a pattern of 50 mm length x 15 mm width to the surface of an oxygen-free copper plate (60 mm x 60 mm x 0.2 mm thickness) by screen printing to form a coating film. The thickness of the metal mask was selected according to the average particle diameter of the hollow glass particles. When the average particle diameter D50 of the hollow glass particles was 150 μm or less, a metal mask with a thickness of 0.12 mm was used, and when the average particle diameter D50 of the hollow glass particles was 150 μm or more, a metal mask with a thickness of 0.30 mm was used. The coating film was dried for 10 minutes in a 120 ° C. blower dryer, and then fired to form a fired film. In addition, as for the firing conditions, when Cu particles were used as the metal particles, the film was fired in a belt-type continuous firing furnace in a nitrogen atmosphere at a temperature of 800 ° C. and a peak holding time of 10 minutes. The total time until discharge was 60 minutes. When Ag particles were used as the metal particles, sintering was carried out in the same manner as in the case of using Cu particles, except that the sintering was carried out in an air atmosphere in a belt-type continuous sintering furnace at a temperature of 600°C.
［焼成膜の観察］
焼成膜をマイクロスコープで観察し、膜の状態を観察した。
[Observation of fired film]
The fired film was observed under a microscope to observe the state of the film.
［焼成膜の元素分析］
焼成膜をＳＥＭ－ＥＤＳ分析により元素分析し、中空ガラス粒子に由来するケイ素が検出されるか確認した。ＳＥＭ－ＥＤＳ分析は、走査型電子顕微鏡（日本電子（株）製「ＪＳＭ－ＩＴ３００ＬＡ」）に付属のエネルギー分散型蛍光Ｘ線分析装置（ＪＥＤ－２３００）を用いた。
[Elemental analysis of fired film]
The fired film was subjected to elemental analysis by SEM-EDS analysis to confirm whether silicon derived from the hollow glass particles was detected. The SEM-EDS analysis was performed using an energy dispersive X-ray fluorescence analyzer (JED-2300) attached to a scanning electron microscope (JSM-IT300LA, manufactured by JEOL Ltd.).
［焼成膜の厚み］
マイクロメーターを用い、銅板と焼成膜との厚み、および銅板のみの厚みを測定し、その差を焼成膜の厚みとした（３カ所の平均値）。膜厚が１２０μｍ以下であれば、適正な薄膜が形成できていると評価した。
[Thickness of fired film]
Using a micrometer, the thickness of the copper plate and the fired film, and the thickness of the copper plate alone were measured, and the difference between them was taken as the thickness of the fired film (average value of three places). If the film thickness was 120 μm or less, it was evaluated that an appropriate thin film had been formed.
［焼成膜の強度（テープ剥離）］
焼成膜の表面にセロテープ（登録商標）を貼り、テープを剥がした後のセロテープの粘着面に、焼成膜や金属粉の付着がないかをマイクロスコープで観察し、以下の判定方法で焼成膜の強度を評価した。
[Strength of fired film (tape peeling)]
Scotch tape (registered trademark) was applied to the surface of the fired film, and after the tape was peeled off, the adhesive surface of the Scotch tape was observed under a microscope to see if any of the fired film or metal powder was attached. The strength of the fired film was evaluated using the following judgment method.
（判定方法）
ａ：テープに何も付着していない（合格）
ｂ：テープに金属粉が付着している（合格）
ｃ：膜自体が剥離する（不合格）。
(Method of Determination)
A: Nothing is attached to the tape (pass)
b: Metal powder is attached to the tape (pass)
c: The film itself peels off (failure).
［焼成膜の強度（鉛筆硬度）］
ＪＩＳ Ｋ５６００－５－４、引っかき硬度（鉛筆法）に準じて、焼成膜の鉛筆硬度を測定した。焼成膜に傷跡が生じなかった最も硬い鉛筆硬度を測定値とし、以下の判定方法で焼成膜の強度を評価した。
[Strength of fired film (pencil hardness)]
The pencil hardness of the fired film was measured according to JIS K5600-5-4, scratch hardness (pencil method). The hardest pencil hardness that did not cause scratches on the fired film was taken as the measured value, and the strength of the fired film was evaluated according to the following judgment method.
（判定方法）
ａ：鉛筆硬度３Ｈ以上（合格）
ｂ：鉛筆硬度Ｈ以上、３Ｈ未満（合格）
ｃ：鉛筆硬度Ｈ未満（不合格）
(Method of Determination)
a: Pencil hardness 3H or higher (pass)
b: Pencil hardness H or more, less than 3H (pass)
c: Pencil hardness less than H (failure)
［焼成膜（多孔質体）の多孔質性（空隙率）］
以下に示す式にて、焼成膜の重量と見掛密度から空隙率を算出し、以下の判定方法で多孔質性を評価した。
[Porosity (porosity) of fired membrane (porous body)]
The porosity was calculated from the weight and apparent density of the fired film using the formula shown below, and the porosity was evaluated using the following judgment method.
焼成膜の重量（ｇ）＝焼成後の評価試料の重量（ｇ）－塗布前の銅板の重量（ｇ）
焼成膜の見掛密度＝焼成膜の重量（ｇ）／（焼成膜の厚み×塗布面積）
焼成膜の空隙率（％）＝１００×（１－焼成膜の見掛密度／金属の真比重）
Weight of fired film (g)=Weight of evaluation sample after firing (g)−Weight of copper plate before coating (g)
Apparent density of fired film = weight of fired film (g) / (thickness of fired film x coating area)
Porosity of fired film (%)=100×(1−apparent density of fired film/true specific gravity of metal)
（判定方法）
ａ：焼成膜の空隙率が７０％以上（合格）
ｂ：焼成膜の空隙率が５０％以上（合格）
ｃ：焼成膜の空隙率が５０％未満（不合格）。
(Method of Determination)
a: The porosity of the fired film is 70% or more (passed)
b: The porosity of the fired film is 50% or more (passed)
c: The porosity of the fired film is less than 50% (failure).
［焼成膜（多孔質体）の吸水性］
焼成膜の縦方向に対して、上端から１０ｍｍ、下端から１０ｍｍの位置にそれぞれ横方向に延びる標線を記し、焼成膜中央部分（対向する標線で区切られた中央領域）の３０ｍｍの距離の範囲を試験範囲とした。水を張ったシャーレを準備し、焼成膜面を上面にして斜め４５度に傾けた評価試料を、焼成膜の下端側の標線まで水中に浸漬し、焼成膜が水を吸い上げる挙動を評価した。詳しくは、下端側の標線から上端側の標線まで３０ｍｍの距離を水が吸い上げられる時間を測定した。測定は３回行い、その平均値を吸い上げ時間とし、以下の判定方法で吸水性を評価した。
[Water absorption of fired membrane (porous body)]
A marking line was drawn 10 mm from the top end and 10 mm from the bottom end of the fired film in the vertical direction, and the test range was a distance of 30 mm from the center of the fired film (the central area separated by the opposing marking lines). A petri dish filled with water was prepared, and an evaluation sample tilted at 45 degrees with the fired film surface facing up was immersed in water up to the marking line on the lower end side of the fired film, and the behavior of the fired film absorbing water was evaluated. In detail, the time it took for water to be absorbed over a distance of 30 mm from the marking line on the lower end side to the marking line on the upper end side was measured. The measurement was performed three times, and the average value was taken as the absorbing time, and the water absorption was evaluated by the following judgment method.
（判定方法）
ａ：水を吸い上げる時間が１０秒以内（合格）
ｂ：水を吸い上げる時間が２０秒以内（合格）
ｃ：水を吸い上げる時間が４０秒以内（合格）
ｄ：水を吸い上げる時間が４０秒以上（不合格）。
(Method of Determination)
A: Time to absorb water is within 10 seconds (pass)
b: Time to absorb water is within 20 seconds (pass)
c: Time to absorb water is within 40 seconds (pass)
d: Time to soak up water is 40 seconds or more (failure).
［総合判定］
焼成膜の強度（テープ剥離、鉛筆硬度）、多孔質性（空隙率）、吸水性（吸い上げ時間）を確認した結果に基づく総合的な判定として、以下の基準で優劣を判定（ランク付け）した。
[Comprehensive judgment]
Based on the results of checking the strength (tape peeling, pencil hardness), porosity (void ratio), and water absorption (wicking time) of the fired films, the films were comprehensively judged (ranked) according to the following criteria.
Ａ：強度、多孔質性、吸水性が全てａ判定（合格）
Ｂ：強度、多孔質性、吸水性がａまたはｂ判定（合格）
Ｃ：強度、多孔質性がａまたはｂ判定、吸水性がｃ判定（合格）
Ｄ：強度、多孔質性、吸水性に不合格の項目がある（不合格）。
A: Strength, porosity, and water absorbency are all rated A (passed)
B: Strength, porosity, and water absorbency are rated a or b (passed)
C: Strength and porosity rated a or b, water absorbency rated c (pass)
D: There are some items that fail in strength, porosity, and water absorbency (fail).
［評価結果］
実施例１～２４および比較例１～９について、配合組成および評価結果を表１～４に示す。比較例１～８は、中空ガラス粒子を含まないペースト組成物を用いた例であり、実施例１～２４および比較例９は、中空ガラス粒子を含むペースト組成物を用いた例である。
[Evaluation results]
The formulations and evaluation results for Examples 1 to 24 and Comparative Examples 1 to 9 are shown in Tables 1 to 4. Comparative Examples 1 to 8 are examples in which a paste composition not containing hollow glass particles was used, and Examples 1 to 24 and Comparative Example 9 are examples in which a paste composition containing hollow glass particles was used.
［実施例１～３、７および比較例１～３、７の結果］
金属粒子として粒子径の小さい球状のＣｕ粒子（Ｃｕ粒子１；平均粒子径Ｄ５０が０．２μｍ、Ｃｕ粒子２；平均粒子径Ｄ５０が０．５μｍ、Ｃｕ粒子３；平均粒子径Ｄ５０が５μｍ）を用いた実施例１～３、比較例１～３を比較した。さらに、金属粒子として粒子径の小さい球状のＡｇ粒子（平均粒径Ｄ５０が１μｍ）を用いた実施例７と比較例７とを比較した。中空ガラス粒子を含まない比較例１～３、７では空隙率が非常に低く、吸水性評価で吸水しなかった。それに対して、中空ガラス粒子１を含む実施例１～３、７（中空ガラス粒子１：金属粒子＝９０：１０の体積比率）では、高い多孔質性（空隙率７０％以上）、高い吸水性（水の吸い上げ時間が２０秒以内）が得られた。
[Results of Examples 1 to 3, 7 and Comparative Examples 1 to 3, 7]
Examples 1 to 3 and Comparative Examples 1 to 3 were compared using spherical Cu particles with small particle diameters (Cu particles 1; average particle diameter D50 of 0.2 μm, Cu particles 2; average particle diameter D50 of 0.5 μm, Cu particles 3; average particle diameter D50 of 5 μm) as the metal particles. Furthermore, Example 7 and Comparative Example 7 were compared using spherical Ag particles with small particle diameters (average particle diameter D50 of 1 μm) as the metal particles. Comparative Examples 1 to 3 and 7, which did not contain hollow glass particles, had a very low porosity and did not absorb water in the water absorption evaluation. In contrast, Examples 1 to 3 and 7, which contained hollow glass particles 1 (volume ratio of hollow glass particles 1:metal particles = 90:10), showed high porosity (porosity of 70% or more) and high water absorption (water uptake time of 20 seconds or less).
比較例１～３、７に対して実施例１～３、７では、中空ガラス粒子の存在により焼成膜の厚みは大きくなったが、焼成膜の強度は優れていたことから、中空ガラス粒子による空洞を含んだまま、金属粒子の焼結構造が強固に形成されたといえる。焼成膜をマイクロスコープで観察したところ、実施例１～３、７では、互いに連なった球状の空隙が無数に存在していたのに対し、比較例１～３、７では、連なった空隙は見られなかった。実施例３および比較例３で得られた焼成膜のマイクロスコープ写真（３００倍）を図１および２に示すが、実施例３では球状の空隙が連なっているのが確認できるのに対して、比較例３では連なった空隙がないことを確認できる。また、焼成膜の元素分析では、比較例１～３、７ではケイ素は検出されなかったのに対し、実施例１～３、７ではケイ素が検出され、焼成膜に中空ガラス粒子が残存していると云える。 Compared to Comparative Examples 1-3 and 7, in Examples 1-3 and 7, the thickness of the fired film was greater due to the presence of hollow glass particles, but the strength of the fired film was excellent, so it can be said that the sintered structure of the metal particles was firmly formed while still containing the cavities caused by the hollow glass particles. When the fired film was observed under a microscope, in Examples 1-3 and 7, countless interconnected spherical voids were present, whereas in Comparative Examples 1-3 and 7, no interconnected voids were observed. Microscope photographs (300x) of the fired films obtained in Example 3 and Comparative Example 3 are shown in Figures 1 and 2. It can be seen that the spherical voids are interconnected in Example 3, whereas in Comparative Example 3, there are no interconnected voids. In addition, in elemental analysis of the fired film, silicon was not detected in Comparative Examples 1-3 and 7, whereas silicon was detected in Examples 1-3 and 7, which indicates that hollow glass particles remain in the fired film.
［比較例８の結果］
比較例３に対して有機ビヒクルを増量した比較例８では、空隙率に差異は無く、固形分濃度が下がったことで焼成膜の厚みが小さくなっただけであった。これより、有機成分の量は空隙率に影響しないと云える。
[Results of Comparative Example 8]
In Comparative Example 8, in which the amount of organic vehicle was increased compared to Comparative Example 3, there was no difference in the porosity, and the thickness of the fired film was reduced only due to the lowered solid content concentration. This shows that the amount of organic components does not affect the porosity.
［実施例４および比較例４の結果］
金属粒子として粒子径の大きい球状のＣｕ粒子４（平均粒径Ｄ５０が６５μｍ）を用いた実施例４と比較例４とを比較した。中空ガラス粒子を含まない比較例４では、焼成膜の強度は大きいが、空隙率が４８％、水の吸い上げ時間が８８秒であったのに対し、中空ガラス粒子１を含む実施例４では、焼成膜の強度が大きく、空隙率が７１％、水の吸い上げ時間が２７秒と多孔質性および吸水性が向上した。
[Results of Example 4 and Comparative Example 4]
Example 4, which used spherical Cu particles 4 with a large particle size (average particle size D50 of 65 μm) as the metal particles, was compared with Comparative Example 4. In Comparative Example 4, which did not contain hollow glass particles, the strength of the fired film was high, but the porosity was 48% and the water absorption time was 88 seconds, whereas in Example 4, which contained hollow glass particles 1, the strength of the fired film was high, the porosity was 71%, and the water absorption time was 27 seconds, resulting in improved porosity and water absorbency.
［実施例５～６および比較例５～６の結果］
金属粒子として樹枝状の電解銅粉（Ｃｕ粒子５；平均粒子径Ｄ５０が２０μｍ）を用いた実施例５と比較例５とを比較した。中空ガラス粒子を含まない比較例５では、金属粒子の樹枝状の形状により、高い多孔質性（空隙率７８％）が得られたものの、吸水性は小さかった（水の吸い上げ時間が５２秒）。それに対して、実施例５では、空隙率が８２％、水の吸い上げ時間が１８秒と多孔質性および吸水性が向上した。
[Results of Examples 5 to 6 and Comparative Examples 5 to 6]
Example 5, which uses dendritic electrolytic copper powder (Cu particles 5; average particle size D50 is 20 μm) as metal particles, was compared with Comparative Example 5. In Comparative Example 5, which does not contain hollow glass particles, high porosity (porosity 78%) was obtained due to the dendritic shape of the metal particles, but water absorption was low (water absorption time 52 seconds). In contrast, Example 5 had a porosity of 82% and a water absorption time of 18 seconds, improving porosity and water absorption.
また、金属粒子として樹枝状の電解銅粉（Ｃｕ粒子６；平均粒子径Ｄ５０が８５μｍ）を用いた実施例６と比較例６とを比較した。中空ガラス粒子を含まない比較例６では、金属粒子の樹枝状の形状により、比較的高い多孔質性（空隙率５５％）が得られたものの、吸水性は小さかった（水の吸い上げ時間が６８秒）。それに対して、実施例６では、空隙率が６８％、水の吸い上げ時間が２８秒と多孔質性および吸水性が向上した。 In addition, Example 6, which uses dendritic electrolytic copper powder (Cu particles 6; average particle size D50: 85 μm) as the metal particles, was compared with Comparative Example 6. In Comparative Example 6, which does not contain hollow glass particles, the dendritic shape of the metal particles results in relatively high porosity (void ratio: 55%), but the water absorption is low (water absorption time: 68 seconds). In contrast, Example 6 has improved porosity and water absorption, with a void ratio of 68% and a water absorption time of 28 seconds.
樹枝状のＣｕ粒子を用いた場合には、Ｃｕ粒子の見掛密度が小さくなり、細かい樹枝形状の枝葉の焼結より高い焼結性が得られ、その結果、多孔質性（空隙率）は高くなるものの、その空隙の大きさが微細なため吸水性は小さくなった。 When dendritic Cu particles were used, the apparent density of the Cu particles was reduced, resulting in a higher sintering property than that of fine dendritic branches and leaves. As a result, although the porosity (void ratio) was increased, the water absorption was reduced because the size of the voids was very small.
［実施例１～７の結果］
なお、実施例１～７の結果から、金属粒子の粒子径と吸水性（および多孔質性）との関係を見ると、粒子径が大きい金属粒子を用いると見掛密度が大きくなるため吸水性（および多孔質性）が低下した。また、粒子径が大きいと焼成膜の厚みが大きくなった。ウィックに好適な薄型化（薄膜化）と高空隙率とが両立した金属多孔質体（焼成膜）を得るという観点では、金属粒子の粒子径は小さい方が好ましく、平均粒子径Ｄ５０は２０μｍ以下が好ましいと云える。
[Results of Examples 1 to 7]
In addition, from the results of Examples 1 to 7, looking at the relationship between the particle size of the metal particles and the water absorption (and porosity), when metal particles with a large particle size are used, the apparent density increases, and the water absorption (and porosity) decreases. In addition, when the particle size is large, the thickness of the fired film increases. From the viewpoint of obtaining a metal porous body (fired film) that is both thin (thin film) and has a high porosity suitable for a wick, it is preferable that the particle size of the metal particles is small, and it can be said that the average particle size D50 is preferably 20 μm or less.
［実施例８～１５、比較例９の結果］
実施例３、比較例３の金属ペースト組成物に対して、中空ガラス粒子（中空ガラス粒子１）と金属粒子（Ｃｕ粒子３）との体積比率を変量した実施例８～１５について、焼成膜の強度、多孔質性（空隙率）、吸水性（吸い上げ時間）を確認した。なお、中空ガラス粒子と金属粒子との体積比率（中空ガラス粒子：金属粒子）を、便宜上「中空ガラス粒子の割合」と記載する。
[Results of Examples 8 to 15 and Comparative Example 9]
The strength, porosity (void ratio), and water absorption (suction time) of the fired film were confirmed for Examples 8 to 15, in which the volume ratio of hollow glass particles (hollow glass particles 1) to metal particles (Cu particles 3) was varied with respect to the metal paste compositions of Example 3 and Comparative Example 3. For convenience, the volume ratio of hollow glass particles to metal particles (hollow glass particles:metal particles) is referred to as the "proportion of hollow glass particles."
中空ガラス粒子を含まない比較例３に対して、中空ガラス粒子の割合を１６：８４（比較例９）、２０：８０（実施例８）、５０：５０（実施例９）、６０：４０（実施例１０）、７０：３０（実施例１１）、８０：２０（実施例１２）、９０：１０（実施例３）、９３：７（実施例１３）、９５：５（実施例１４）、９７：３（実施例１５）の順に増加させた。その結果、比較例３に対して中空ガラス粒子の割合が増加すると、焼成膜の厚みが大きくなるとともに、焼成膜の強度を保持したまま吸水性（および多孔質性）が向上する傾向が見られた。但し、中空ガラス粒子の割合が少ない比較例９（１６：８４）では多孔質性および吸水性が不合格の水準であり、実施例８の割合（２０：８０）以上の場合に多孔質性および吸水性が合格の水準になった。 Compared to Comparative Example 3, which does not contain hollow glass particles, the ratio of hollow glass particles was increased in the following order: 16:84 (Comparative Example 9), 20:80 (Example 8), 50:50 (Example 9), 60:40 (Example 10), 70:30 (Example 11), 80:20 (Example 12), 90:10 (Example 3), 93:7 (Example 13), 95:5 (Example 14), and 97:3 (Example 15). As a result, when the ratio of hollow glass particles was increased compared to Comparative Example 3, the thickness of the fired film increased and the water absorption (and porosity) tended to improve while maintaining the strength of the fired film. However, in Comparative Example 9 (16:84), which has a low ratio of hollow glass particles, the porosity and water absorption were at an unacceptable level, and when the ratio was equal to or greater than that of Example 8 (20:80), the porosity and water absorption were at an acceptable level.
特に、中空ガラス粒子の割合が８０：２０（実施例１２）、９０：１０（実施例３）の場合に吸水時間が１０秒以内となり、特に吸水性に優れた。さらに、中空ガラス粒子の割合を増加させた実施例１３（９３：７）、実施例１４（９５：５）、実施例１５（９７：３）では、多孔質性（空隙率）が高くなりすぎて、焼成膜の強度が若干低下するとともに、吸水性も若干低下する傾向が見られたが、実用的には問題の無いレベルであった。 In particular, when the ratio of hollow glass particles was 80:20 (Example 12) and 90:10 (Example 3), the water absorption time was within 10 seconds, and water absorption was particularly excellent. Furthermore, in Examples 13 (93:7), 14 (95:5), and 15 (97:3), in which the ratio of hollow glass particles was increased, the porosity (void ratio) became too high, and the strength of the fired film tended to decrease slightly, as well as the water absorption, but this was at a level that would not be a problem in practical use.
［実施例１６～２４の結果］
実施例３の金属ペースト組成物に対して、中空ガラス粒子の割合を９０：１０と一定にしたまま、金属粒子に対する中空ガラス粒子の平均粒子径Ｄ５０を１２～１８０μｍの範囲で変量した実施例１６～２４について、焼成膜の強度、多孔質性（空隙率）、吸水性（吸い上げ時間）を確認した。
[Results of Examples 16 to 24]
For the metal paste composition of Example 3, the ratio of hollow glass particles was kept constant at 90:10, but the average particle diameter D50 of the hollow glass particles relative to the metal particles was varied in the range of 12 to 180 μm in Examples 16 to 24, and the strength, porosity (void ratio), and water absorption (wicking time) of the fired film were confirmed.
中空ガラス粒子の平均粒子径Ｄ５０を、１２μｍ（実施例１６）、２０μｍ（実施例１７）、３５μｍ（実施例１８）、４０μｍ（実施例１９）、６０μｍ（実施例２０）、８０μｍ（実施例３）、１００μｍ（実施例２１）、１２０μｍ（実施例２２）、１５０μｍ（実施例２３）、１８０μｍ（実施例２４）の順に増加させた。 The average particle diameter D50 of the hollow glass particles was increased in the following order: 12 μm (Example 16), 20 μm (Example 17), 35 μm (Example 18), 40 μm (Example 19), 60 μm (Example 20), 80 μm (Example 3), 100 μm (Example 21), 120 μm (Example 22), 150 μm (Example 23), and 180 μm (Example 24).
焼成膜の形成については、平均粒子径Ｄ５０が１２～１２０μｍの範囲の場合（実施例３、実施例１６～２２）には、厚さ０．１２ｍｍのメタルマスクを用いたスクリーン印刷が可能であった。実施例３、実施例２１、実施例２２で用いた中空ガラス粒子は、平均粒子径Ｄ９０の値が１２０μｍ（メタルマスクの厚み）以上の粒子を含むが、スキージの撓みで粒子を乗り越えられる程度であり、成膜性に問題は無かった。中空ガラス粒子は焼成により溶融し、中空ガラス粒子としての形状を失うため、実施例３、実施例１６～２２では中空ガラス粒子の粒子径に関わらず、焼成膜の厚みは全て１２０μｍ以下で同程度であった。 When the average particle diameter D50 was in the range of 12 to 120 μm (Example 3, Examples 16 to 22), it was possible to perform screen printing using a metal mask with a thickness of 0.12 mm to form the fired film. The hollow glass particles used in Examples 3, 21, and 22 included particles with an average particle diameter D90 of 120 μm (the thickness of the metal mask) or more, but the particles could be overcome by the bending of the squeegee, and there were no problems with film formation. The hollow glass particles melt when fired and lose their shape as hollow glass particles, so in Examples 3 and 16 to 22, the thickness of the fired film was all approximately the same, at 120 μm or less, regardless of the particle diameter of the hollow glass particles.
一方、中空ガラスの平均粒子径Ｄ５０が１５０μｍ以上（実施例２３、実施例２４）の場合には、厚さ０．１２ｍｍのメタルマスクでは、スクリーン印刷の際に粒子がスキージに引きずられた跡が残り成膜性が低かったため、厚さ０．３ｍｍのメタルマスクを用いた。その結果、焼成膜の厚みが２７０μｍ程度に大きくなったため、薄膜化は難しいと云える。 On the other hand, when the average particle diameter D50 of the hollow glass was 150 μm or more (Examples 23 and 24), a metal mask with a thickness of 0.3 mm was used because a 0.12 mm thick metal mask left traces of the particles being dragged by the squeegee during screen printing, resulting in poor film formation. As a result, the thickness of the fired film was as large as about 270 μm, making it difficult to make it thinner.
焼成膜の強度、空隙率、吸水性については、中空ガラス粒子の平均粒子径Ｄ５０が１２～１８０μｍの範囲の場合、いずれの実施例でも、焼成膜の強度は高い水準であり、吸水性（および多孔質性）についても実用上問題の無いレベルであった。 Regarding the strength, porosity, and water absorption of the fired film, when the average particle diameter D50 of the hollow glass particles was in the range of 12 to 180 μm, the strength of the fired film was at a high level in all examples, and the water absorption (and porosity) was at a level that did not pose any practical problems.
最も小さい平均粒子径Ｄ５０が１２μｍの中空ガラス粒子を用いた実施例１６では、空隙率は高いものの、空隙の大きさが小さすぎるためか、水の吸い上げ時間が２６秒と吸水性が若干劣った（判定ｃ）。一方、最も大きい平均粒子径Ｄ５０が１８０μｍの中空ガラス粒子を用いた実施例２４では、空隙率が高かったが、空隙が大きくなりすぎたためか、水の吸い上げ時間が２２秒と吸水性が若干劣った（判定ｃ）。 In Example 16, which used hollow glass particles with the smallest average particle diameter D50 of 12 μm, the porosity was high, but the water absorption time was 26 seconds, which was slightly inferior to the water absorption, possibly because the pores were too small (Judgment c). On the other hand, in Example 24, which used hollow glass particles with the largest average particle diameter D50 of 180 μm, the porosity was high, but the water absorption time was 22 seconds, which was slightly inferior to the water absorption, possibly because the pores were too large (Judgment c).
平均粒子径Ｄ５０が２０～１５０μｍの中空ガラス粒子を用いた実施例１７～２３、実施例３では、水の吸い上げ時間が２０秒以内と吸水性にも優れているため、適度な空隙率の金属多孔質体が形成される平均粒子径（Ｄ５０）の範囲と推察できる。特に、平均粒子径Ｄ５０が６０～１００μｍの中空ガラス粒子を用いた実施例２０、実施例３、実施例２１では、水の吸い上げ時間が１０秒以内の高い吸水性が得られ、最も好適な空隙率の金属多孔質体が形成される平均粒子径（Ｄ５０）の範囲と推察できる。 In Examples 17 to 23 and Example 3, which used hollow glass particles with an average particle diameter D50 of 20 to 150 μm, the water absorption time was within 20 seconds, which was excellent in terms of water absorption, and it can be inferred that this is the average particle diameter (D50) range in which a metal porous body with an appropriate porosity is formed. In particular, in Examples 20, 3, and 21, which used hollow glass particles with an average particle diameter D50 of 60 to 100 μm, high water absorption was achieved with a water absorption time of within 10 seconds, and it can be inferred that this is the average particle diameter (D50) range in which a metal porous body with the most suitable porosity is formed.
実施例２２で得られた焼成膜のマイクロスコープ写真（３００倍）を図３に示す。実施例３で得られた焼成膜のスコープ写真（図１）と比較すると、実施例３よりも粒径が大きい中空ガラス粒子を用いた実施例２２では、図１よりも大きい球状の空隙が連なっているのが確認できる。 Figure 3 shows a microscope photograph (300x) of the fired film obtained in Example 22. When compared with the microscope photograph (Figure 1) of the fired film obtained in Example 3, it can be seen that in Example 22, which uses hollow glass particles with a larger particle size than in Example 3, larger spherical voids than those in Figure 1 are connected together.
本発明のペースト組成物は、薄型（薄膜）で空隙率の高い金属多孔質体として利用でき、各種の分野で利用できる。なかでも、ヒートパイプやベーパーチャンバーの構成部材、例えば、筐体の外壁層、内壁層、内壁部に付設または積層されるウィック（多孔質体による毛細管状構造体）、内部に付設する他の構成部材として利用でき、通液性にも優れるため、ウィックとして好適に利用できる。 The paste composition of the present invention can be used as a thin (thin film) metal porous body with high porosity, and can be used in various fields. In particular, it can be used as a component of a heat pipe or vapor chamber, for example, a wick (a capillary structure made of a porous body) attached or laminated to the outer wall layer, inner wall layer, or inner wall portion of a housing, or other component attached to the inside, and since it has excellent liquid permeability, it can be suitably used as a wick.
Claims (8)
中空ガラス粒子、金属粒子および有機ビヒクルを含み、かつ前記中空ガラス粒子と、前記金属粒子との体積比率が、前者：後者＝７０：３０～９７：３であるペースト組成物。 A paste composition for forming a porous body having a porosity of 70 to 98%, comprising:
A paste composition comprising hollow glass particles, metal particles and an organic vehicle, the volume ratio of the hollow glass particles to the metal particles being from 70:30 to 97:3.
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| JP2008169426A (en) | 2007-01-11 | 2008-07-24 | Aida Kagaku Kogyo Kk | Composition of lightweight precious metal to be sintered, sintered body of lightweight precious metal, and method for manufacturing sintered body of lightweight precious metal |
| WO2009144792A1 (en) | 2008-05-28 | 2009-12-03 | 相田化学工業株式会社 | Composition for precious metal sintering, process for producing precious metal sinter and precious metal sinter |
| CN107552796A (en) | 2017-09-26 | 2018-01-09 | 成都新柯力化工科技有限公司 | A kind of method that foam metal is prepared by resin microsphere accumulation |
| JP2020070481A (en) | 2018-11-02 | 2020-05-07 | トヨタ自動車株式会社 | Method for producing aluminum structure having independent holes |
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| WO2009144792A1 (en) | 2008-05-28 | 2009-12-03 | 相田化学工業株式会社 | Composition for precious metal sintering, process for producing precious metal sinter and precious metal sinter |
| CN107552796A (en) | 2017-09-26 | 2018-01-09 | 成都新柯力化工科技有限公司 | A kind of method that foam metal is prepared by resin microsphere accumulation |
| JP2020070481A (en) | 2018-11-02 | 2020-05-07 | トヨタ自動車株式会社 | Method for producing aluminum structure having independent holes |
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