JP6665399B2 - Zinc oxide particles, method for producing the same and use thereof - Google Patents
Zinc oxide particles, method for producing the same and use thereof Download PDFInfo
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- JP6665399B2 JP6665399B2 JP2016026350A JP2016026350A JP6665399B2 JP 6665399 B2 JP6665399 B2 JP 6665399B2 JP 2016026350 A JP2016026350 A JP 2016026350A JP 2016026350 A JP2016026350 A JP 2016026350A JP 6665399 B2 JP6665399 B2 JP 6665399B2
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- Prior art keywords
- zinc oxide
- oxide particles
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- heat
- polyhedral
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- 239000011787 zinc oxide Substances 0.000 title claims description 189
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- 238000001493 electron microscopy Methods 0.000 claims description 3
- 238000007561 laser diffraction method Methods 0.000 claims description 3
- 238000000790 scattering method Methods 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
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Images
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- Compositions Of Macromolecular Compounds (AREA)
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Description
本発明は、酸化亜鉛粒子及びその製造方法並びにその用途に関する。 The present invention relates to zinc oxide particles, a method for producing the same, and uses thereof.
酸化亜鉛は、白色顔料、紫外線遮蔽材、充填剤、高熱伝導性材料、赤外線反射材料、吸着剤、光触媒、触媒、セラミックス原料、導電材、圧電材料、ガスセンサー、電子写真感光材料、バリスタ、蛍光体、エミッタ、電子デバイス等種々の用途に用いられており、また、化粧料、外用剤、塗料、グリース、樹脂組成物等に配合して用いられている。 Zinc oxide is white pigment, ultraviolet shielding material, filler, high thermal conductive material, infrared reflective material, adsorbent, photocatalyst, catalyst, ceramic raw material, conductive material, piezoelectric material, gas sensor, electrophotographic photosensitive material, varistor, fluorescence It is used for various uses such as body, emitter, electronic device, etc., and is used by being blended in cosmetics, external preparations, paints, greases, resin compositions and the like.
酸化亜鉛はその製造において、ｐＨ値を調整したり、有機物を添加したりするなどの製造条件を種々変化させることにより、様々な形状の粒子を製造可能であることが知られている。 It is known that zinc oxide can produce particles of various shapes by varying the production conditions such as adjusting the pH value or adding an organic substance in the production thereof.
例えば、特許文献１には、六角形面のわたり径が０．５〜４０μｍで垂直方向の高さが０．０５〜２０μｍにある六角柱状形状酸化亜鉛が開示されている。また、特許文献２には、一次粒子径が１．１μｍ以上であり、粒度分布におけるＤ９０／Ｄ１０が３．０以下である六角板状酸化亜鉛粒子が開示されている。特許文献３には、多層構造を有する１０μｍ程度の六角錐状／六角板状酸化亜鉛結晶が開示されている。特許文献４には、メジアン径が０．１μｍ以上の四面体状及び／又は四面体対状酸化亜鉛粒子が開示されている。 For example, Patent Document 1 discloses a hexagonal columnar zinc oxide having a hexagonal surface with a diameter of 0.5 to 40 μm and a vertical height of 0.05 to 20 μm. Patent Document 2 discloses hexagonal plate-shaped zinc oxide particles having a primary particle diameter of 1.1 μm or more and a D90 / D10 in the particle size distribution of 3.0 or less. Patent Literature 3 discloses a hexagonal pyramid / hexagonal plate-shaped zinc oxide crystal having a multilayer structure and having a thickness of about 10 μm. Patent Document 4 discloses tetrahedral and / or tetrahedral zinc oxide particles having a median diameter of 0.1 μm or more.
酸化亜鉛粒子はそれぞれの用途に応じて、形状、大きさ、結晶性等の制御が求められている。例えば、充填剤、セラミックス原料等に用いる場合は、嵩が低く、充填性のよい酸化亜鉛が求められている。また、光触媒、触媒、セラミックス原料、導電材、圧電材料、高熱伝導性材料等に用いる場合は、充填性に加えて結晶性のよい酸化亜鉛が求められている。また、化粧料、外用剤、塗料、グリース、樹脂組成物等に配合して組成物として用いる場合は、該組成物が充分な流動性を示すような酸化亜鉛が求められている。 Control of the shape, size, crystallinity, etc. of the zinc oxide particles is required according to the respective applications. For example, when used as a filler, a ceramic raw material, etc., zinc oxide having low bulk and good filling properties is required. In addition, when used as a photocatalyst, a catalyst, a ceramic raw material, a conductive material, a piezoelectric material, a high heat conductive material, and the like, zinc oxide having good crystallinity in addition to filling properties is required. In addition, when the composition is used as a composition by being added to a cosmetic, an external preparation, a paint, a grease, a resin composition, or the like, zinc oxide is required so that the composition exhibits sufficient fluidity.
前述の特許文献１〜４に代表されるような多面体形状を有する酸化亜鉛は、嵩が低くて充填性がよいものの、組成物として用いる場合に実用上充分な流動性が得られず、組成物が扱い難くなったり、加工が行い難くなったりするという問題があった。 Although zinc oxide having a polyhedral shape as represented by the above-mentioned Patent Documents 1 to 4 has a low bulk and a good filling property, when used as a composition, practically sufficient fluidity cannot be obtained, so that the composition However, there is a problem that it becomes difficult to handle and processing becomes difficult.
本発明者らは、多面体形状を有する酸化亜鉛粒子について、嵩が低く充填性がよいという長所を生かしつつ、組成物として用いた場合に実用上充分な流動性を示すことができる酸化亜鉛粒子を鋭意検討した結果、表面部が特定の形態をとる多面体形状酸化亜鉛粒子とすることにより上記課題を解決できることなどを見出し、本発明を完成した。 The present inventors have developed a zinc oxide particle having a polyhedral shape, which can exhibit practically sufficient fluidity when used as a composition, while taking advantage of its low bulk and good filling properties. As a result of intensive studies, they have found that the above problems can be solved by using polyhedral zinc oxide particles whose surface portion has a specific form, and have completed the present invention.
すなわち、本発明は、
（１）多面体形状であって、多面体を構成する隣接する面同士の稜線及び頂点に相当する部分が曲面で構成されている角丸多面体形状酸化亜鉛粒子である。
That is, the present invention
(1) Rounded polyhedral shaped zinc oxide particles having a polyhedral shape, in which portions corresponding to ridges and vertices between adjacent surfaces constituting the polyhedron are curved surfaces.
（２）前記多面体形状が六角柱状である（１）の角丸多面体形状酸化亜鉛粒子である。 (2) The rounded polyhedral shaped zinc oxide particles according to (1), wherein the polyhedral shape is a hexagonal prism.
（３）電子顕微鏡法で測定した六角形の面の平均わたり径Ｌ（μｍ）と、六角形の面に略垂直方向の高さＨ（μｍ）とのアスペクト比Ｈ／Ｌが０．５〜２である請求項２に記載の角丸多面体形状酸化亜鉛粒子である。 (3) The aspect ratio H / L between the average diameter L (μm) of the hexagonal surface measured by electron microscopy and the height H (μm) substantially perpendicular to the hexagonal surface is from 0.5 to 0.5. 3. The rounded polyhedral shaped zinc oxide particles according to claim 2, which is 2.
（４）レーザー回折／散乱法で測定したメジアン径Ｒが１〜１００μｍである（１）〜（３）のいずれかに記載の角丸多面体形状酸化亜鉛粒子である。 (4) The rounded polyhedral zinc oxide particles according to any one of (1) to (3), wherein the median diameter R measured by a laser diffraction / scattering method is 1 to 100 μm.
（５）タップ密度が２ｇ／ｃｍ３以上である（１）〜（４）のいずれかに記載の角丸多面体形状酸化亜鉛粒子である。 (5) The rounded polyhedral shaped zinc oxide particles according to any one of (1) to (4), wherein the tap density is 2 g / cm 3 or more.
（６）多面体形状を基本形状とし、その表面に錐台状、瘤状又は鱗状から選ばれる少なくとも一種類の凸部が複数存在する外観である（１）〜（５）のいずれかに記載の角丸多面体形状酸化亜鉛粒子である。 (6) The appearance according to any one of (1) to (5), wherein the polyhedron shape is a basic shape, and a plurality of at least one type of protrusion selected from a frustum shape, a bump shape, and a scale shape is present on the surface thereof. It is a rounded polyhedral shaped zinc oxide particle.
（７）表面に有機化合物及び／又は無機化合物を含む被覆を有する（１）〜（６）のいずれかに記載の角丸多面体形状酸化亜鉛粒子である。 (7) The rounded polyhedral shaped zinc oxide particles according to any one of (1) to (6), having a coating containing an organic compound and / or an inorganic compound on the surface.
（８）（１）〜（７）に記載の角丸多面体形状酸化亜鉛粒子と、メジアン径の異なる他のフィラーを含む混合粉末である。 (8) A mixed powder comprising the rounded polyhedral zinc oxide particles described in (1) to (7) and another filler having a different median diameter.
（９）多面体形状酸化亜鉛粒子を酸又はアルカリと接触させる、酸化亜鉛粒子の製造方法である。 (9) A method for producing zinc oxide particles, wherein the polyhedral zinc oxide particles are brought into contact with an acid or an alkali.
（１０）（１）〜（７）のいずれかに記載の酸化亜鉛粒子又は（８）に記載の混合粉末を含む化粧料である。 (10) A cosmetic comprising the zinc oxide particles according to any one of (1) to (7) or the mixed powder according to (8).
（１１）（１）〜（７）のいずれかに記載の酸化亜鉛粒子又は（８）に記載の混合粉末を含む塗料組成物である。 (11) A coating composition comprising the zinc oxide particles according to any one of (1) to (7) or the mixed powder according to (8).
（１２）（１）〜（７）のいずれかに記載の酸化亜鉛粒子又は（８）に記載の混合粉末を含む樹脂組成物である。 (12) A resin composition containing the zinc oxide particles according to any one of (1) to (7) or the mixed powder according to (8).
（１３）（１）〜（７）のいずれかに記載の酸化亜鉛粒子又は（８）に記載の混合粉末を含む放熱性組成物である。 (13) A heat dissipation composition comprising the zinc oxide particles according to any one of (1) to (7) or the mixed powder according to (8).
（１４）更に、メジアン径が異なる他の放熱フィラーを含む（１３）に記載の放熱性組成物である。 (14) The heat dissipating composition according to (13), further including another heat dissipating filler having a different median diameter.
本発明の酸化亜鉛粒子は角丸多面体形状であるため、充填性がよく、且つ、組成物として用いた場合に実用上充分な流動性を示す。例えば、化粧料、外用剤、塗料、グリース、繊維、樹脂組成物等に充填剤、白色顔料、熱伝導材料等として配合する際に、あるいはセラミックス原料、導電材等に使用する際に、高濃度（高充填率）としても実用上充分な流動性を確保することができ、酸化亜鉛の特性を充分活用することができる。具体例を挙げると、化粧料に配合したときに、肌へのすべり感がよくなる。別の例では、放熱性組成物に配合すると、高い充填率でもハンドリングや加工が容易な粘度とすることができる。付随して、更に充填率を高めても実用的な粘度範囲を保つことができるため、より熱伝導率の高い放熱性組成物が得られる。 Since the zinc oxide particles of the present invention have a rounded polyhedral shape, they have good filling properties and exhibit practically sufficient fluidity when used as a composition. For example, when blended in cosmetics, external preparations, paints, greases, fibers, resin compositions, etc. as fillers, white pigments, heat conductive materials, etc., or when used as ceramic raw materials, conductive materials, etc. (High filling rate) can ensure sufficient fluidity for practical use, and the properties of zinc oxide can be fully utilized. As a specific example, when blended in a cosmetic, the feeling of slip on the skin is improved. In another example, when blended with a heat-radiating composition, the viscosity can be easily handled and processed even at a high filling rate. Concomitantly, even if the filling rate is further increased, a practical viscosity range can be maintained, so that a heat dissipating composition having higher thermal conductivity can be obtained.
また、前記アスペクト比Ｈ／Ｌが特定の範囲にある六角柱状酸化亜鉛粒子の場合、角丸形状を持つことにより、同一充填率としたときであっても、特異的に熱伝導率が高まる。 Further, in the case of hexagonal columnar zinc oxide particles having an aspect ratio H / L within a specific range, by having a rounded shape, the thermal conductivity is specifically increased even at the same filling rate.
本発明の酸化亜鉛は、六方晶、立方晶、立方晶面心構造いずれかのＸ線回折パターンを示すＺｎＯを少なくとも５０質量％含むものであり、水酸化亜鉛や製造の際に使用する硫酸亜鉛、硝酸亜鉛、塩化亜鉛、酢酸亜鉛等の亜鉛化合物が含まれていてもよい。また、製造の際に使用する亜鉛化合物を構成していた硫酸根、硝酸根、塩素、酢酸等が含まれていてもよく、また、カルボン酸、その塩、アミン化合物等の材料が含まれていてもよい。 The zinc oxide of the present invention contains at least 50% by mass of ZnO exhibiting an X-ray diffraction pattern of any of hexagonal, cubic, and cubic face-centered structures, and includes zinc hydroxide and zinc sulfate used in the production. And zinc compounds such as zinc nitrate, zinc chloride and zinc acetate. Further, it may contain a sulfate group, a nitrate group, chlorine, acetic acid and the like which constitute the zinc compound used in the production, and may contain a material such as a carboxylic acid, a salt thereof, and an amine compound. You may.
本発明の酸化亜鉛粒子の特徴である角丸多面体形状とは、該多面体を構成する隣接する面同士の稜線（辺）及び頂点に相当する部分が曲面で構成されているものをいう。別の表現をすると、多面体形状粒子の平面部の一部は維持しつつ多面体の角が丸まった形状とも言え、４つ以上の複数の平面とそれらをつなぐ曲面に囲まれた立体とも言える。なお、酸化亜鉛粒子全体の全ての稜線や頂点に相当する部分が曲面になっている必要はなく、一部が稜線や頂点として存在していてもよい。 The rounded polyhedron shape, which is a feature of the zinc oxide particles of the present invention, refers to a shape in which portions corresponding to ridges (sides) and vertices of adjacent surfaces constituting the polyhedron are curved surfaces. In other words, it can be said that the polyhedron-shaped particles have a shape in which the corners of the polyhedron are rounded while a part of the plane portion is maintained, and that the solid is surrounded by four or more planes and a curved surface connecting them. Note that all the ridges and vertices of the zinc oxide particles do not need to be curved surfaces, and some may be present as ridges and vertices.
多面体としては例えば、正多面体、半正多面体、デルタ多面体、角柱、反角柱、角錐、双角錐、角錐柱、菱面体及びそれらの複合体や集合体などが挙げられるが、これらに限定されない。また、角柱等のいわゆる底面を持つものについて、その底面形状には例えば、三角形、四角形、六角形、八角形などが挙げられるが、これらに限定されない。本発明でいう多面体形状とは、前述の多面体形状を基本形状として、その一部の形状が変更されていたり、多面体に別の微細構造が付加されているような形状であっても、およそ多面体形状であると認識可能なものも含む。 Examples of the polyhedron include, but are not limited to, a regular polyhedron, a semiregular polyhedron, a delta polyhedron, a prism, an anti-prism, a pyramid, a dipyramid, a pyramid, a rhombohedron, and a complex or aggregate thereof. In addition, for a prism having a so-called bottom surface such as a prism, the bottom shape includes, for example, a triangle, a quadrangle, a hexagon, and an octagon, but is not limited thereto. The polyhedron shape referred to in the present invention refers to the above-mentioned polyhedron shape as a basic shape, a shape in which a part of the shape is changed, or a shape in which another microstructure is added to the polyhedron. Also includes those that can be recognized as shapes.
酸化亜鉛粒子が多面体形状であると、球状粒子と比べて酸化亜鉛粒子を多く充填することができるものの、粒子同士の稜線や頂点が干渉し合うため流動性に劣る。そこで本発明のように多面体の稜線や頂点相当部が曲面で構成されている形状の角丸多面体形状酸化亜鉛粒子を用いることで、組成物中において、稜線や頂点が接触したときの粒子同士の干渉が抑制され、粒子自体の動きに自由度が増すことから、組成物の流動性を向上させることができる。その結果、例えば、化粧料に配合すると、肌へのすべり感がよくなり、別の例では、放熱性組成物に配合すると、酸化亜鉛粒子の配合量が多くても実用上充分な流動性、具体的には１０〜５００Ｐａ・ｓ／１ｒｐｍ程度の領域の粘度とすることができる。また、角丸多面体形状粒子はある程度平面部を有しているため、多面体形状の粒子の持つ良好な充填性という特徴も併せ持っている。そのため、放熱性組成物に配合すると、組成物の熱伝導性と流動性を高度に両立できる。 When the zinc oxide particles have a polyhedral shape, the zinc oxide particles can be filled more than the spherical particles, but the ridge lines and vertices of the particles interfere with each other, resulting in poor fluidity. Therefore, by using the rounded polyhedral shaped zinc oxide particles having a shape in which the ridges and vertices of the polyhedron are configured as curved surfaces as in the present invention, in the composition, the particles when the ridges and vertices come into contact with each other are used. Since the interference is suppressed and the degree of freedom in the movement of the particles themselves is increased, the fluidity of the composition can be improved. As a result, for example, when incorporated into cosmetics, the feeling of slip on the skin is improved, and in another example, when incorporated into a heat-dissipating composition, practically sufficient fluidity, even when the amount of zinc oxide particles is large, Specifically, the viscosity can be in the range of about 10 to 500 Pa · s / 1 rpm. Further, since the rounded polyhedral particles have a flat surface to some extent, they also have the characteristic of good filling properties of the polyhedral particles. Therefore, when blended with a heat-dissipating composition, the composition can be highly compatible with both thermal conductivity and fluidity.
本発明の角丸多面体形状酸化亜鉛粒子は、特に六角柱状を基本とする形状であると好ましい。面の数が多い場合は流動性の点では有利であるが、充填性の点では不利になる。六角柱状であると、該六角柱を構成する隣接する面同士の稜線（辺）及び頂点に相当する部分を曲面で構成した形態としたときに、充填性と流動性のバランスがより高まるため好ましい。ここで、「六角柱状」とは、一般的に六角板状、六角短柱状、六角棒状と呼ばれる形状を含む。また、これら以外にも、六角柱を基本形状として、その一部の形状が変更されていたり、六角柱に別の微細構造が付加された形状であって、大まかには六角柱状であると認識できるものも含む。例えば、六角柱状の柱部の中央部にくびれがあり、その部分の径は両端部に比べ小さい粒子、いわゆる鼓状粒子であってもよい。 The rounded polyhedral shaped zinc oxide particles of the present invention preferably have a hexagonal column shape. When the number of surfaces is large, it is advantageous in terms of fluidity, but disadvantageous in terms of filling. The hexagonal column shape is preferable because the balance between the filling property and the fluidity is further enhanced when the portions corresponding to the ridges (sides) and the vertices of the adjacent surfaces constituting the hexagonal column are formed as curved surfaces. . Here, the “hexagonal column shape” includes shapes generally called a hexagonal plate shape, a hexagonal short columnar shape, and a hexagonal rod shape. In addition to these, it is recognized that hexagonal prisms have a basic shape, some of which have been changed in shape, or other microstructures have been added to hexagonal prisms, and are roughly hexagonal prisms. Including what can be done. For example, the hexagonal column portion may have a constriction at the center portion, and the diameter of the portion may be smaller than that at both ends, so-called drum-shaped particles.
本発明の角丸多面体形状酸化亜鉛粒子が角丸六角柱状粒子である場合、六角形の面の平均わたり径Ｌ（μｍ）と、六角形の面に略垂直方向の高さＨ（μｍ）とのアスペクト比Ｈ／Ｌが０．５以上であると好ましい。Ｈ／Ｌをこの範囲とした角丸六角柱状粒子は角丸でない同範囲の六角柱状粒子と比較して、タップ密度を高くすることができ、特に、充填率が同じであっても熱伝導率を著しく高くすることができる。また、この範囲とすることで、組成物に配合したときの組成物の流動性を更に高めることができる。その結果、化粧料に配合すると、肌へのすべり感がよくなる。また、組成物の粘度をある一定値に合わせようとする場合、酸化亜鉛粒子の配合量を多くすることができる。その結果、放熱性組成物に配合すると、酸化亜鉛粒子の配合量を多くしても流動性を維持することができ、組成物の熱伝導性と流動性をより高度に両立できる。Ｈ／Ｌの上限は２程度とすると特に前記効果が高いため好ましい。Ｈ／Ｌは０．７〜１．５の範囲であると特に好ましい。 When the rounded polyhedral shaped zinc oxide particles of the present invention are rounded hexagonal columnar particles, the average crossing diameter L (μm) of the hexagonal surface and the height H (μm) substantially perpendicular to the hexagonal surface are obtained. Is preferably 0.5 or more. The rounded hexagonal column-shaped particles having H / L in this range can increase the tap density as compared with the hexagonal column-shaped particles in the same range which are not rounded. Can be significantly increased. In addition, when the content is in this range, the fluidity of the composition when blended with the composition can be further enhanced. As a result, when incorporated into cosmetics, the feeling of slipping on the skin is improved. When the viscosity of the composition is to be adjusted to a certain value, the amount of the zinc oxide particles can be increased. As a result, when incorporated into the heat-dissipating composition, the fluidity can be maintained even when the amount of zinc oxide particles is increased, and the thermal conductivity and the fluidity of the composition can be more compatible. It is preferable to set the upper limit of H / L to about 2 because the effect is particularly high. H / L is particularly preferably in the range of 0.7 to 1.5.
前記「わたり径」とは、六角形の面の「対向する頂点を結ぶ線の長さ」のことを言う。また、「高さ」とは、「六角形の面に略垂直方向の高さ」を言い、六角柱の縦の長さを言う。前記寸法は電子顕微鏡法で求めることができる。具体的には、酸化亜鉛粒子の平均わたり径Ｌ（μｍ）、平均高さＨ（μｍ）は、少なくとも２０個の粒子の六角面のわたり径、高さを電子顕微鏡写真から計測して、下記式によって算出した平均わたり径、平均高さとする。
平均わたり径＝Σ（Ｌｎ・ｎ）／Σｎ
平均高さ＝Σ（Ｈｎ・ｎ）／Σｎ
上記式中、ｎは計測した個々の粒子の番号を表し、Ｌｎは第ｎ番目の粒子のわたり径、Ｈｎは第ｎ番目の粒子の高さをそれぞれ表す。
The “crossing diameter” refers to “the length of a line connecting opposing vertices” of a hexagonal surface. Further, “height” refers to “height in a direction substantially perpendicular to a hexagonal surface” and refers to the vertical length of a hexagonal prism. The dimensions can be determined by electron microscopy. Specifically, the average diameter L (μm) and the average height H (μm) of the zinc oxide particles are determined by measuring the hexagonal diameter and height of at least 20 particles from an electron micrograph. The average diameter and the average height calculated by the formulas are used.
Mean Watari diameter = Σ (L n · n) / Σn
Average height = Σ (H n · n) / Σn
In the above formulas, n represents the number of individual particles measured, L n spans the diameter of the n-th particle, it is H n represent respectively the height of the n-th particle.
本発明の酸化亜鉛粒子の多面体を構成する各面は、必ずしも平坦な面でなくてもよい。角丸多面体形状を基本形状とし、その平面部や稜線部に錐台状、瘤状又は鱗状から選ばれる少なくとも一種類の凸部が存在する外観である。このような凸部は他の凸部と重なり合わないように単独で存在してもよく、積層していてもよく、特に、互いの位置を少しずつずらしながら凸部が積層している態様であってもよい。このような凸部についても、その輪郭が明確な錐台状や鱗状でなくてもよく、輪郭が曲面で構成された（角が取れた）形状、瘤状であってもよい。そのような形状の例として、図８に角丸六角柱状酸化亜鉛粒子の走査電子顕微鏡写真を示す。 Each surface constituting the polyhedron of the zinc oxide particles of the present invention is not necessarily a flat surface. This is an appearance in which a rounded polyhedron shape is used as a basic shape, and at least one type of protrusion selected from a frustum shape, a bump shape, and a scale shape is present on a plane portion or a ridge line portion. Such protrusions may be present alone so as not to overlap with other protrusions, or may be stacked, particularly in a mode in which the protrusions are stacked while slightly shifting their positions. There may be. The shape of such a convex portion may not be a frustum or a scale having a clear contour, but may be a curved shape (sharp corner) or a bump. FIG. 8 shows a scanning electron micrograph of rounded hexagonal columnar zinc oxide particles as an example of such a shape.
本発明の角丸多面体形状酸化亜鉛粒子は、レーザー回折／散乱法で測定したメジアン径Ｒが１〜１００μｍであると好ましい。Ｒがこの範囲内であれば、特に流動性が高くハンドリング性に優れた組成物を得ることができる。シート状の製品等の厚みに制約がある用途に使用する場合などもあるので、Ｒは用途に応じて適宜設定してよい。Ｒが４０μｍ以下であれば幅広い用途に用いることができるため好ましい。 The rounded polyhedral shaped zinc oxide particles of the present invention preferably have a median diameter R of 1 to 100 μm as measured by a laser diffraction / scattering method. When R is within this range, a composition having particularly high fluidity and excellent handling properties can be obtained. R may be appropriately set according to the use since it may be used in applications where the thickness of a sheet-shaped product or the like is restricted. It is preferable that R is 40 μm or less because it can be used for a wide range of applications.
本発明の酸化亜鉛粒子は、ＪＩＳ Ｒ １６３９−２に従い測定を行ったタップ密度が２ｇ／ｃｍ３以上とすると好ましく、酸化亜鉛の真密度（５．６ｇ／ｃｍ３程度）を考慮すると、２〜５．５ｇ／ｃｍ３の範囲であることが好ましい。この範囲とすると、より嵩が低くまた充填性のよい酸化亜鉛粒子となり、充填剤、セラミックス原料、光触媒、触媒、セラミックス原料、導電材、圧電材料、高熱伝導性材料等に用いる場合に好適である。例えば、このような角丸多面体形状で、且つ、タップ密度が高い酸化亜鉛粒子は、粒子同士が接触し易く、粒子間で熱を伝導し易くなる。更に、組成物への酸化亜鉛粒子充填率を高くすることができるという利点があり、組成物の熱伝導性を一層高めることができる。 The zinc oxide particles of the present invention preferably have a tap density measured in accordance with JIS R 1639-2 of 2 g / cm 3 or more, and in consideration of the true density of zinc oxide (about 5.6 g / cm 3 ), 2 to 2. It is preferably in the range of 5.5 g / cm 3 . Within this range, zinc oxide particles having lower bulk and good filling properties are obtained, and are suitable for use as fillers, ceramic raw materials, photocatalysts, catalysts, ceramic raw materials, conductive materials, piezoelectric materials, high heat conductive materials, and the like. . For example, zinc oxide particles having such a rounded polyhedral shape and a high tap density are easy for the particles to come into contact with each other and to conduct heat easily between the particles. Furthermore, there is an advantage that the zinc oxide particle filling rate in the composition can be increased, and the thermal conductivity of the composition can be further enhanced.
本発明の酸化亜鉛粒子は、粉末Ｘ線回折法で算出した平均結晶子径ｒ（μｍ）が、０．０５０〜０.１２０μｍの範囲であると好ましく、０．０８０〜０.１００μｍの範囲であるとより好ましい。このような結晶性の高い酸化亜鉛は、光触媒、触媒、セラミックス原料、導電材、圧電材料、高熱伝導性材料等に用いる場合に好適である。平均結晶子径ｒは、Ｒｉｇａｋｕ社製試料水平型多目的Ｘ線回折装置（Ｕｌｔｉｍａ ＩＶ）を用いて測定したＸ線回折パターンに基づき、シェラーの式を用いて算出する。 The zinc oxide particles of the present invention preferably have an average crystallite diameter r (μm) calculated by a powder X-ray diffraction method in the range of 0.050 to 0.120 μm, and more preferably in the range of 0.080 to 0.100 μm. It is more preferable to have them. Such zinc oxide having high crystallinity is suitable for use as a photocatalyst, a catalyst, a ceramic raw material, a conductive material, a piezoelectric material, a high heat conductive material, or the like. The average crystallite diameter r is calculated using Scherrer's formula based on an X-ray diffraction pattern measured using a sample horizontal multipurpose X-ray diffractometer (Ultima IV) manufactured by Rigaku.
本発明の角丸多面体形状酸化亜鉛粒子を、本酸化亜鉛粒子と異なる他のフィラーとの混合物としてもよい。特に本酸化亜鉛粒子とはメジアン径が異なる他のフィラーを用いた混合物とすると、組成物としたときの流動性を高めることができるため好ましい。他のフィラーとしては特に限定されず、公知のものを任意に用いることができる。例えば、酸化亜鉛、酸化マグネシウム、酸化チタン、酸化アルミニウム、酸化ジルコニウムなどの金属酸化物、窒化アルミニウム、窒化ホウ素、炭化ケイ素、窒化ケイ素、窒化チタン、金属シリコン、金属粒子、炭素化合物（ダイヤモンド、グラファイト、グラフェン、カーボンナノチューブなど）等を挙げることができる。他のフィラーは、一種類に限定されず、複数種類のフィラーを併用してもよい。他のフィラーの形状には特に制限がなく、球状、粒状、立方体状、棒状、六角板状、鱗片状、不定形状を挙げることができる。また、これらのフィラーにも、後述の無機化合物や有機化合物の被覆を施してもよい。 The rounded polyhedral zinc oxide particles of the present invention may be a mixture of the zinc oxide particles and another filler different from the zinc oxide particles. In particular, it is preferable to use a mixture using another filler having a different median diameter from the zinc oxide particles, since the fluidity of the composition can be enhanced. The other filler is not particularly limited, and a known filler can be arbitrarily used. For example, metal oxides such as zinc oxide, magnesium oxide, titanium oxide, aluminum oxide, and zirconium oxide, aluminum nitride, boron nitride, silicon carbide, silicon nitride, titanium nitride, metal silicon, metal particles, carbon compounds (diamond, graphite, Graphene, carbon nanotube, etc.). The other filler is not limited to one type, and a plurality of types of fillers may be used in combination. The shape of the other filler is not particularly limited, and examples thereof include a spherical shape, a granular shape, a cubic shape, a rod shape, a hexagonal plate shape, a scale shape, and an irregular shape. These fillers may be coated with an inorganic compound or an organic compound described below.
本発明の角丸多面体形状酸化亜鉛粒子を放熱フィラーとして用いる場合には、本酸化亜鉛粒子と異なる他の放熱フィラーとの混合物としてもよい。特に本酸化亜鉛粒子とはメジアン径が異なる他の放熱フィラーを用いた混合物とすると、放熱性組成物としたときの流動性と熱伝導性を高めることができるため好ましい。他の放熱フィラーとしては特に限定されず、熱伝導性を有するものであれば公知のものを任意に用いることができる。例えば、酸化亜鉛、酸化マグネシウム、酸化チタン、酸化アルミニウム、酸化ジルコニウムなどの金属酸化物、窒化アルミニウム、窒化ホウ素、炭化ケイ素、窒化ケイ素、窒化チタン、金属シリコン、金属粒子、炭素化合物（ダイヤモンド、グラファイト、グラフェン、カーボンナノチューブなど）等を挙げることができる。他の放熱フィラーは、一種類に限定されず、複数種類の放熱フィラーを併用してもよい。他の放熱フィラーの形状には特に制限がなく、球状、粒状、立方体状、棒状、六角板状、鱗片状、不定形状を挙げることができる。また、これらの放熱フィラーにも、後述の無機化合物や有機化合物の被覆を施してもよい。 When the rounded polyhedral shaped zinc oxide particles of the present invention are used as a heat-radiating filler, a mixture of the zinc oxide particles and another heat-radiating filler different from the zinc oxide particles may be used. In particular, it is preferable to use a mixture using another heat-radiating filler having a different median diameter from the zinc oxide particles, since the fluidity and thermal conductivity of the heat-radiating composition can be increased. The other heat radiation filler is not particularly limited, and any known heat radiation filler may be used as long as it has thermal conductivity. For example, metal oxides such as zinc oxide, magnesium oxide, titanium oxide, aluminum oxide, and zirconium oxide, aluminum nitride, boron nitride, silicon carbide, silicon nitride, titanium nitride, metal silicon, metal particles, carbon compounds (diamond, graphite, Graphene, carbon nanotube, etc.). The other heat radiation fillers are not limited to one type, and a plurality of types of heat radiation fillers may be used in combination. The shape of the other heat radiation filler is not particularly limited, and examples thereof include a spherical shape, a granular shape, a cubic shape, a rod shape, a hexagonal plate shape, a scale shape, and an irregular shape. Further, these heat radiation fillers may be coated with an inorganic compound or an organic compound described below.
本発明の角丸多面体形状酸化亜鉛粒子を粒子径の大きい主放熱フィラーとして用いる場合には、メジアン径Ｒは５〜１００μｍとするのが好ましく、５〜４０μｍとするとより好ましい。主放熱フィラーとして角丸多面体形状酸化亜鉛粒子を使用すると、樹脂等の媒体への充填性が良好（高い充填率での配合が可能）であり、放熱性組成物中に熱伝導パスが形成され易いため、熱伝導は生じ易く、良好に放熱することができる。また、組成物に配合したときに、粒子の表面エネルギーが小さいため、樹脂等になじみ易くなる結果、組成物の流動性を確保できる。この場合、小粒径の副放熱フィラーの粒子径は、主放熱フィラーのメジアン径Ｒに対して、Ｒ／４０〜Ｒ／２（μｍ）の範囲とすると好ましい。このような小粒径放熱フィラーを併用することで、主放熱フィラーの隙間を埋めることができる。ひいては、放熱性組成物への充填性を高めることができ、熱伝導性を向上させることができる。加えて、主放熱フィラーの隙間に小粒径放熱フィラーが介在することで、これらが潤滑剤の役割を果たし、放熱性組成物の流動性をより維持し易くすることができる。本発明の酸化亜鉛粒子と小粒径放熱フィラーとの配合比率には特に制限がなく、適宜調整することができ、例えば、体積比で７：３〜９：１の範囲が好適である。 When the rounded polyhedral zinc oxide particles of the present invention are used as the main heat-radiating filler having a large particle diameter, the median diameter R is preferably 5 to 100 μm, and more preferably 5 to 40 μm. When the rounded polyhedral zinc oxide particles are used as the main heat-radiating filler, the filling property of the resin or other medium into the medium is good (can be blended at a high filling rate), and a heat-conducting path is formed in the heat-radiating composition. Therefore, heat conduction easily occurs, and heat can be radiated well. Further, when incorporated into the composition, the surface energy of the particles is small, so that the particles easily become compatible with a resin or the like, so that the fluidity of the composition can be ensured. In this case, it is preferable that the particle diameter of the sub heat radiation filler having a small particle diameter is in the range of R / 40 to R / 2 (μm) with respect to the median diameter R of the main heat radiation filler. By using such a small-diameter heat-radiating filler in combination, the gap between the main heat-radiating fillers can be filled. As a result, it is possible to enhance the filling property of the heat-dissipating composition and to improve the thermal conductivity. In addition, since the small-diameter heat-radiating filler is interposed between the main heat-radiating fillers, they function as a lubricant, and the fluidity of the heat-radiating composition can be more easily maintained. The mixing ratio of the zinc oxide particles of the present invention to the small-diameter heat-radiating filler is not particularly limited and can be adjusted as appropriate. For example, a volume ratio of 7: 3 to 9: 1 is preferable.
一方、本発明の角丸多面体形状酸化亜鉛粒子を粒子径の小さい副放熱フィラーとして用いる場合には、メジアン径Ｒは１〜１０μｍとするのが好ましい。副放熱フィラーとして角丸多面体形状酸化亜鉛粒子を使用すると、組成物に配合したときに、粒子の表面エネルギーが小さいため、樹脂等になじみ易くなる結果、組成物の流動性を確保できる。この場合、大粒径の主放熱フィラーの粒子径は、副放熱フィラーのメジアン径Ｒに対して２Ｒ〜４０Ｒ（μｍ）の範囲とすると好ましい。本発明の角丸多面体形状酸化亜鉛粒子を副放熱フィラーとして使用することで、主放熱フィラーの隙間を埋めることができる。ひいては、放熱性組成物への充填性を高めることができ、熱伝導性を向上させることができる。加えて、主放熱フィラーの隙間に副放熱フィラーが介在することで、これらが潤滑剤の役割を果たし、放熱性組成物の流動性をより維持し易くすることができる。大粒径の主放熱フィラーと本発明の酸化亜鉛粒子との配合比率には特に制限がなく、適宜調整することができ、例えば、体積比で７：３〜９：１の範囲が好適である。 On the other hand, when the rounded polyhedral shaped zinc oxide particles of the present invention are used as a sub-radiating filler having a small particle diameter, the median diameter R is preferably 1 to 10 μm. When the rounded polyhedral zinc oxide particles are used as the auxiliary heat-radiating filler, the surface energy of the particles is small when blended in the composition, so that the particles are easily adapted to a resin or the like, so that the fluidity of the composition can be secured. In this case, the particle diameter of the main heat radiation filler having a large particle diameter is preferably in the range of 2R to 40R (μm) with respect to the median diameter R of the sub heat radiation filler. By using the rounded polyhedral shaped zinc oxide particles of the present invention as the auxiliary heat radiating filler, the gap between the main heat radiating fillers can be filled. As a result, it is possible to enhance the filling property of the heat-dissipating composition and to improve the thermal conductivity. In addition, since the auxiliary heat radiating filler is interposed in the gap between the main heat radiating fillers, they function as a lubricant, and the fluidity of the heat radiating composition can be more easily maintained. There are no particular restrictions on the mixing ratio of the main heat-radiating filler having a large particle diameter and the zinc oxide particles of the present invention, and the mixing ratio can be appropriately adjusted. For example, a volume ratio of 7: 3 to 9: 1 is preferable. .
本発明の酸化亜鉛粒子は、前記Ｒと粉末Ｘ線回折法で求めた平均結晶子径ｒ（μｍ）との比Ｒ／ｒが４０〜２００であると好ましい。本発明の酸化亜鉛粒子は多結晶体であるため、粒子内に存在する結晶粒界が熱伝導等の性能を阻害する障壁として作用してしまう。従って、たとえ粒子径が大きい粒子であっても結晶粒界が多く存在してしまうと粒子径に見合うだけの熱伝導率の向上が発現しなくなる。Ｒ／ｒは粒子内における結晶粒界の平均存在数の指標であり、Ｒ／ｒを２００以下とすることで、熱伝導の粒界障壁を減少させ、粒子自体の熱伝導性を高めることができる。ただし、Ｒ／ｒはＲを小さくすることによっても小さくなり、Ｒが小さくなると粒子の充填性低下や凝集により組成物としたときの熱伝導性が低下してしまうため、Ｒ／ｒは４０以上であると好ましい。 The zinc oxide particles of the present invention preferably have a ratio R / r of R to an average crystallite diameter r (μm) determined by a powder X-ray diffraction method of 40 to 200. Since the zinc oxide particles of the present invention are polycrystalline, crystal grain boundaries existing in the particles act as barriers that hinder performance such as heat conduction. Therefore, even if the particles have a large particle diameter, if there are many crystal grain boundaries, the improvement in thermal conductivity corresponding to the particle diameter will not be exhibited. R / r is an index of the average number of crystal grain boundaries present in the particles. By setting R / r to 200 or less, it is possible to reduce the grain boundary barrier of heat conduction and increase the thermal conductivity of the particles themselves. it can. However, R / r is also reduced by reducing R, and when R is reduced, the thermal conductivity when the composition is reduced due to a decrease in the packing property of the particles and agglomeration. Is preferable.
次に、本発明は、多面体形状酸化亜鉛粒子を酸又はアルカリと接触させる、酸化亜鉛粒子の製造方法である。こうした処理を行うことで、多面体形状酸化亜鉛粒子の平面部をある程度残しながら、多面体を構成する隣接する面同士の稜線及び頂点に相当する部分が溶解して曲面状になった角丸多面体形状に変化する。その結果、酸化亜鉛粒子同士の干渉が抑制され、組成物の流動性を高めることができる。 Next, the present invention is a method for producing zinc oxide particles, which comprises contacting polyhedral zinc oxide particles with an acid or an alkali. By performing such a process, a part corresponding to the ridges and vertices of adjacent surfaces constituting the polyhedron is melted into a rounded polyhedron shape having a curved surface shape, while leaving a flat surface portion of the polyhedral shape zinc oxide particles to some extent. Change. As a result, interference between the zinc oxide particles is suppressed, and the fluidity of the composition can be increased.
多面体形状酸化亜鉛粒子と酸又はアルカリとを接触させる方法には特に制限はなく、公知の方法を用いることができる。例えば、多面体形状酸化亜鉛粒子の分散液に酸又はアルカリを添加する方法が挙げられる。また、低濃度の酸又はアルカリ溶液中に、多面体形状酸化亜鉛粒子やその分散液を一括で添加する方法でも可能である。 The method for bringing the polyhedral zinc oxide particles into contact with an acid or an alkali is not particularly limited, and a known method can be used. For example, a method of adding an acid or an alkali to a dispersion of polyhedral zinc oxide particles may be used. Alternatively, a method in which polyhedral zinc oxide particles and a dispersion thereof are added all at once to a low-concentration acid or alkali solution is also possible.
多面体形状酸化亜鉛粒子の分散液は、多面体形状酸化亜鉛粒子の粉末と溶媒を混合し、分散させることで得ることができる。多面体形状酸化亜鉛粒子を含むケーキと溶媒を混合し、分散させることでも得ることができる。 The dispersion of the polyhedral zinc oxide particles can be obtained by mixing and dispersing the powder of the polyhedral zinc oxide particles and a solvent. It can also be obtained by mixing and dispersing a cake containing polyhedral shaped zinc oxide particles and a solvent.
分散液の溶媒には特に制限はなく、任意の液体を用いてよい。例えば、水系溶媒又はアルコール等の有機溶媒を用いることができる。水系溶媒を用いると有機溶媒含有の廃液が発生しないため好ましい。 The solvent of the dispersion is not particularly limited, and any liquid may be used. For example, an aqueous solvent or an organic solvent such as alcohol can be used. The use of an aqueous solvent is preferable because no waste liquid containing an organic solvent is generated.
分散液中の酸化亜鉛粒子の濃度は２５０ｇ／Ｌ以下の範囲とするのが好ましい。この範囲とすることで、酸又はアルカリと接触させた際に、元の多面体形状をある程度維持しながら、稜線及び頂点が選択的に溶解された、角丸多面体形状の粒子が得られ易い。濃度がこの範囲を超えると、反応の際に形状が崩れた粒子が発生し易くなる。 The concentration of the zinc oxide particles in the dispersion is preferably in the range of 250 g / L or less. By setting the content in this range, it is easy to obtain rounded polyhedral particles in which the ridge lines and vertices are selectively dissolved while maintaining the original polyhedral shape to some extent when brought into contact with an acid or an alkali. If the concentration exceeds this range, particles having a deformed shape during the reaction are likely to be generated.
添加する酸又はアルカリの態様は特に制限がなく、固体状、液体状、気体状等、任意の状態でよい。添加量を制御し易いという理由で、酸又はアルカリを溶媒に溶解させたものを用いるのが好ましい。溶媒には水、有機溶媒が挙げられる。経済性、環境負荷の観点から水を用いることが好ましい。 The form of the acid or alkali to be added is not particularly limited, and may be in any state such as solid, liquid, and gas. It is preferable to use a solution in which an acid or an alkali is dissolved in a solvent because the amount of addition is easily controlled. Solvents include water and organic solvents. It is preferable to use water from the viewpoint of economy and environmental load.
酸としては、無機酸、有機酸を使用することができる。無機酸としては、塩酸、硝酸、硫酸、リン酸などが挙げられる。有機酸としては、酢酸、クエン酸、シュウ酸などのカルボン酸化合物やメタンスルホン酸、ベンゼンスルホン酸、p-トルエンスルホン酸、フルオロスルホン酸などのスルホン酸化合物が挙げられる。酸としては、無機酸を用いるのが反応後の廃液処理の観点から好ましく、中でも、硫酸が二価の酸で添加量を抑えることができ、かつ低価格であるため、コストの観点から特に好ましい。 As the acid, an inorganic acid or an organic acid can be used. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and the like. Examples of the organic acid include carboxylic acid compounds such as acetic acid, citric acid, and oxalic acid, and sulfonic acid compounds such as methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and fluorosulfonic acid. As the acid, it is preferable to use an inorganic acid from the viewpoint of waste liquid treatment after the reaction. Among them, sulfuric acid is particularly preferable from the viewpoint of cost because sulfuric acid can be suppressed in the amount of addition with a divalent acid and is inexpensive. .
水溶液とする場合の酸の濃度は硫酸に換算して０．５〜７０質量％の範囲であると好ましい。特に、２〜１０質量％の範囲であると、元の多面体形状をある程度維持しながら、稜線及び頂点が選択的に溶解された、角丸多面体形状の粒子が得られ易いという点でより好ましい。濃度がこの範囲を超えると、反応の際に形状が崩れた粒子が発生し易くなる。濃度がこの範囲より低いと、反応が遅くなり、生産効率が落ちる。 The acid concentration in the case of an aqueous solution is preferably in the range of 0.5 to 70% by mass in terms of sulfuric acid. In particular, when the content is in the range of 2 to 10% by mass, rounded polyhedron-shaped particles in which ridge lines and vertices are selectively melted while maintaining the original polyhedron shape to some extent are more preferable. If the concentration exceeds this range, particles having a deformed shape during the reaction are likely to be generated. If the concentration is lower than this range, the reaction will be slow and the production efficiency will be reduced.
酸化亜鉛粒子分散液に酸性水溶液を添加する場合、酸の添加速度には特に制限はなく、分散液中の酸化亜鉛粒子の濃度や酸性水溶液の濃度、生産効率等を考慮して任意に設定してよい。例えば０〜３６０分としてよい。添加速度が遅いほうが、元の多面体形状を維持し、且つ、稜線及び頂点が選択的に溶解された、角丸多面体形状の粒子が得られ易い。分散液中の酸化亜鉛粒子の濃度や酸性水溶液の濃度が高いときも、添加速度は遅めのほうが好ましい。生産効率と粒子形状を考慮すると、１０〜１２０分が好ましく、３０〜９０分がより好ましい。添加中は必要に応じて撹拌を行ってもよい。 When adding an acidic aqueous solution to the zinc oxide particle dispersion, the rate of addition of the acid is not particularly limited, and may be arbitrarily set in consideration of the concentration of the zinc oxide particles in the dispersion, the concentration of the acidic aqueous solution, the production efficiency, and the like. May be. For example, the time may be 0 to 360 minutes. When the addition rate is lower, it is easier to obtain rounded polyhedral particles in which the original polyhedral shape is maintained and the ridges and vertices are selectively dissolved. Even when the concentration of the zinc oxide particles or the concentration of the acidic aqueous solution in the dispersion is high, the addition rate is preferably slow. In consideration of the production efficiency and the particle shape, the time is preferably 10 to 120 minutes, more preferably 30 to 90 minutes. During the addition, stirring may be performed if necessary.
酸と酸化亜鉛を接触させる温度は４０℃以下とするのが好ましい。特に、２０〜３０℃の範囲であると、元の多面体形状をある程度維持しながら、稜線及び頂点が選択的に溶解された、角丸多面体形状の粒子が得られ易いという点でより好ましい。温度が高いと、反応の際に形状が崩れた粒子が発生し易くなる。温度が低すぎると反応が遅くなり、生産効率が落ちる。 The temperature at which the acid and zinc oxide are brought into contact is preferably 40 ° C. or lower. In particular, it is more preferable that the temperature is in the range of 20 to 30 ° C., since it is easy to obtain rounded polyhedral particles in which ridge lines and vertices are selectively dissolved while maintaining the original polyhedral shape to some extent. When the temperature is high, particles having a deformed shape during the reaction are likely to be generated. If the temperature is too low, the reaction will be slow and production efficiency will decrease.
酸化亜鉛粒子と酸とを水系溶媒中で反応させるとき、反応中のｐＨは６〜８の範囲で維持するのが好ましい。この範囲とすると、元の多面体形状をある程度維持しながら、稜線及び頂点が選択的に溶解された、角丸多面体形状の粒子が得られ易く、また、溶解させた亜鉛イオンの再析出を防げるという理由で好ましい。特にｐＨ７付近が好ましい。 When reacting zinc oxide particles with an acid in an aqueous solvent, the pH during the reaction is preferably maintained in the range of 6 to 8. With this range, while maintaining the original polyhedral shape to some extent, the ridges and vertices are selectively dissolved, it is easy to obtain rounded polyhedral shaped particles, and it is possible to prevent re-precipitation of the dissolved zinc ions. Preferred for reasons. Particularly, pH around 7 is preferable.
添加する酸の量は、Ｈ＋として、ＺｎＯに対し１０〜２５モル％とすると好ましい。この範囲の添加量で前記反応条件を調整することにより、元の多面体形状を維持し、且つ、稜線及び頂点が選択的に溶解された、角丸多面体形状の粒子が得られ易い。添加する酸の量が多すぎると、過度に酸化亜鉛粒子が溶解し、多面体形状が維持しづらくなる。添加する酸の量が少なすぎると、稜線及び頂点が残存し易くなる。 The amount of the acid to be added is preferably 10 to 25 mol% with respect to ZnO as H + . By adjusting the reaction conditions with the added amount in this range, it is easy to obtain rounded polyhedral particles in which the original polyhedral shape is maintained and the ridge lines and vertices are selectively dissolved. If the amount of the acid to be added is too large, the zinc oxide particles are excessively dissolved, making it difficult to maintain the polyhedral shape. When the amount of the acid to be added is too small, ridge lines and vertices tend to remain.
アルカリとしては、水酸化ナトリウムや水酸化カリウム等の公知のアルカリ化合物を使用することができる。酸化亜鉛粒子をアルカリと接触させて角丸多面体形状の酸化亜鉛粒子を製造する場合、添加するアルカリの量は、ＯＨ−として、ＺｎＯに対し４０〜１００モル％とすると好ましい。また、アルカリと酸化亜鉛を接触させる温度は４０℃以上とするのが好ましい。アルカリ水溶液を用いる場合の濃度やその添加速度は適宜調整することができる。 Known alkali compounds such as sodium hydroxide and potassium hydroxide can be used as the alkali. When the zinc oxide particles are brought into contact with an alkali to produce rounded polyhedral zinc oxide particles, the amount of the alkali to be added is preferably OH − and is preferably 40 to 100 mol% based on ZnO. The temperature at which the alkali and the zinc oxide are brought into contact is preferably set to 40 ° C. or higher. The concentration and the rate of addition in the case of using an alkaline aqueous solution can be appropriately adjusted.
酸でもアルカリでも角丸多面体形状酸化亜鉛粒子は製造可能であるが、水酸化物などの沈殿物の生成や添加量を抑えることができること、材料使用量などの経済的な理由から、酸を用いるのが好ましい。 The rounded polyhedral zinc oxide particles can be produced with an acid or an alkali, but the acid is used because of economical reasons such as the ability to suppress the generation and addition of precipitates such as hydroxides and the amount of materials used. Is preferred.
このようにして得られた酸化亜鉛粒子は、必要に応じて濾過・洗浄して固液分離し、乾燥、乾式粉砕を行う。固液分離手段には特に制限はなく、重力濾過、加圧濾過、真空濾過、吸引濾過、遠心濾過、自然沈降などの手段をとり得る。工業的には加圧濾過、真空濾過、吸引濾過が好ましく、脱水能力が高く大量に処理できるので、フィルタープレス、ロールプレス等の濾過機を用いるのが好ましい。乾燥にはバンド式ヒーター、バッチ式ヒーター、噴霧乾燥機等を用いることができる。乾燥温度は適宜設定することができるが、８０〜２００℃程度が適当である。乾式粉砕には、ハンマーミル、ピンミル等の衝撃粉砕機、ローラーミル、パルペライザー、解砕機等の摩砕粉砕機、ロールクラッシャー、ジョークラッシャー等の圧縮粉砕機、ジェットミル等の気流粉砕機等を用いることができる。 The zinc oxide particles thus obtained are filtered and washed as necessary, separated into solid and liquid, and dried and dry-pulverized. The solid-liquid separation means is not particularly limited, and may be a means such as gravity filtration, pressure filtration, vacuum filtration, suction filtration, centrifugal filtration, or natural sedimentation. Industrially, pressure filtration, vacuum filtration, and suction filtration are preferable, and a filter such as a filter press or a roll press is preferably used because it has a high dehydration ability and can be processed in a large amount. For drying, a band heater, a batch heater, a spray dryer, or the like can be used. The drying temperature can be appropriately set, but is preferably about 80 to 200 ° C. For the dry pulverization, an impact pulverizer such as a hammer mill and a pin mill, a grinding pulverizer such as a roller mill, a pulperizer, and a pulverizer, a compression pulverizer such as a roll crusher and a jaw crusher, and an air pulverizer such as a jet mill are used. be able to.
原料となる多面体形状酸化亜鉛粒子の製造方法には特に制限はなく、公知の方法を用いることができる。例えば、特開２０１４−１４８５６８号公報の方法で六角柱状形状酸化亜鉛を製造できる。ＷＯ２０１５／１１８７７７パンフレットに記載の方法で六角板状酸化亜鉛粒子を製造できる。特開２０１３−２４５１３９号公報の方法で六角錐状／六角板状酸化亜鉛結晶を製造できる。ＷＯ２０１３／１３３４１１パンフレットに記載の方法で四面体状及び／又は四面体対状酸化亜鉛粒子を製造できる。メジアン径が５μｍ以上の六角柱状酸化亜鉛粒子は、例えば、以下の方法により製造できる。層状亜鉛化合物を、塩基性化合物の存在下で、溶液中で加熱、熟成させることで製造することができる。具体的には、Ｚｎ４ＳＯ４（ＯＨ）６・５Ｈ２Ｏの組成式で表される層状亜鉛化合物の水溶液に、塩基性化合物として好ましいアミン化合物（例えばモノエタノールアミン）を添加し、撹拌機で撹拌しながら、好ましくは９０℃以上溶媒の沸点以下の温度条件下４〜１２時間かけて熟成する。アミン化合物の添加量は、層状亜鉛化合物の亜鉛原子に対するモル比で表して、０．２〜１．０の範囲であることが好ましい。なお、Ｚｎ４ＳＯ４（ＯＨ）６・５Ｈ２Ｏの組成式で表される層状亜鉛化合物は、公知の各種製法（例えば、特開２００７−２２３８７３号、特開平５−０７０１２４号、あるいは特開昭５４−３８２９８号などに記載の方法）によって得ることができる。また、上記層状亜鉛化合物は鉱物として天然に存在するので、これを用いることもできる。 The method for producing the polyhedral zinc oxide particles as the raw material is not particularly limited, and a known method can be used. For example, hexagonal column-shaped zinc oxide can be manufactured by the method of JP-A-2014-148568. Hexagonal plate-like zinc oxide particles can be produced by the method described in WO2015 / 118777 pamphlet. Hexagonal pyramid / hexagonal plate-shaped zinc oxide crystals can be produced by the method disclosed in JP-A-2013-245139. Tetrahedral and / or tetrahedral zinc oxide particles can be produced by the method described in WO2013 / 133411. Hexagonal columnar zinc oxide particles having a median diameter of 5 μm or more can be produced, for example, by the following method. The layered zinc compound can be produced by heating and aging in a solution in the presence of a basic compound. More specifically, the aqueous solution of Zn 4 SO 4 (OH) 6 · 5H 2 O composition layered zinc compounds of the formula was added preferably an amine compound as the basic compound (e.g., monoethanolamine), stirrer While stirring at a temperature of 90 ° C. or higher and the boiling point of the solvent for 4 to 12 hours. The amount of the amine compound added is preferably in the range of 0.2 to 1.0 in terms of the molar ratio to the zinc atom of the layered zinc compound. Incidentally, Zn 4 SO 4 (OH) 6 · 5H 2 O composition layered zinc compound represented by the formula, various known method (e.g., JP 2007-223873, JP-A-5-070124, or JP 54-38298). Further, since the layered zinc compound exists naturally as a mineral, it can be used.
また、必要に応じて前記の酸化亜鉛粒子を焼成してもよい。焼成条件は特に限定されないが、焼成温度を３００〜１５００℃、焼成時間は１０分〜１０時間程度が適当である。焼成は静置焼成で行ってもよく回転式の炉内で行ってもよい。静置焼成は、ムライト製、ムライト・コージライト製の匣鉢中で行うことができる。焼成は通常、空気、酸素、窒素等の雰囲気下で行うことができる。それらの気体のフロー下で行ってもよい。このような焼成処理によって、メジアン径を殆ど変化させずに結晶子径を大きくすることができ、酸化亜鉛粒子の熱伝導性を更に高めることができる。酸化亜鉛粒子の焼成は、７００〜１２００℃で焼成することが好ましく、８５０〜１２００℃の温度で焼成することがより好ましい。焼成温度が高いほど結晶子径が大きくなり易く、酸化亜鉛粒子の熱伝導性をより一層高めることができる。焼成処理は、酸又はアルカリと接触させた後で行ってもよく、それに先立って行ってもよい。 Further, the zinc oxide particles may be fired as needed. The firing conditions are not particularly limited, but a firing temperature of 300 to 1500 ° C. and a firing time of about 10 minutes to 10 hours are appropriate. The firing may be performed by stationary firing or in a rotary furnace. The stationary firing can be performed in a sagger made of mullite or mullite cordierite. The firing can be usually performed in an atmosphere of air, oxygen, nitrogen or the like. It may be performed under the flow of those gases. By such a baking treatment, the crystallite diameter can be increased without substantially changing the median diameter, and the thermal conductivity of the zinc oxide particles can be further increased. The firing of the zinc oxide particles is preferably performed at 700 to 1200 ° C, more preferably at 850 to 1200 ° C. The higher the firing temperature, the larger the crystallite diameter is likely to be, and the thermal conductivity of the zinc oxide particles can be further increased. The baking treatment may be performed after contacting with an acid or an alkali, or may be performed prior thereto.
本発明の酸化亜鉛粒子は、その粒子表面に必要に応じてケイ素、チタン、アルミニウム、ジルコニウム、スズ等の酸化物あるいはそれらのリン酸塩等の無機化合物の被覆層を設けることもできる。これらの無機化合物は１種を用いても、２種以上を積層又は混合して用いてもよい。また、溶媒、塗料やプラスチックス等への分散性を付与するなどの目的で、有機化合物を被覆してもよく、前記の無機化合物と有機化合物の両者を被覆してもよい。有機化合物としては、例えば、（１）有機ケイ素化合物（（ａ）オルガノポリシロキサン類（ジメチルポリシロキサン、メチル水素ポリシロキサン、メチルメトキシポリシロキサン、メチルフェニルポリシロキサン、ジメチルポリシロキサンジオール、ジメチルポリシロキサンジハイドロジェン等又はそれらの共重合体）、（ｂ）オルガノシラン類（アミノシラン、エポキシシラン、メタクリルシラン、ビニルシラン、メルカプトシラン、クロロアルキルシラン、アルキルシラン、フルオロアルキルシラン等又はそれらの加水分解生成物）、（ｃ）オルガノシラザン類（ヘキサメチルシラザン、ヘキサメチルシクロトリシラザン等）等）、
（２）有機金属化合物（（ａ）有機チタニウム化合物（アミノアルコキシチタニウム、リン酸エステルチタニウム、カルボン酸エステルチタニウム、スルホン酸エステルチタニウム、チタニウムキレート、亜リン酸エステルチタニウム錯体等）、（ｂ）有機アルミニウム化合物（アルミニウムキレート等）、（ｃ）有機ジルコニウム化合物（カルボン酸エステルジルコニウム、ジルコニウムキレート等）等）、
（３）ポリオール類（トリメチロールプロパン、トリメチロールエタン、ペンタエリスリトール等）、
（４）アルカノールアミン類（モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノプロパノールアミン、ジプロパノールアミン、トリプロパノールアミン等）又はその誘導体（酢酸塩、シュウ酸塩、酒石酸塩、ギ酸塩、安息香酸塩等の有機酸塩等）、
（５）高級脂肪酸類（ステアリン酸、ラウリン酸、オレイン酸等）又はその金属塩（アルミニウム塩、亜鉛塩、マグネシウム塩、カルシウム塩、バリウム塩等）、
（６）高級炭化水素類（パラフィンワックス、ポリエチレンワックス等）又はその誘導体（パーフルオロ化物等）が挙げられる。これらの有機化合物は１種を用いても、２種以上を積層又は混合して用いてもよい。無機化合物、有機化合物の被覆量は、酸化亜鉛粒子に対し、０．１〜５０質量％の範囲が好ましく、０．１〜３０質量％の範囲が更に好ましい。
酸化亜鉛粒子の粒子表面に前記の無機化合物や有機化合物を被覆させるには、酸化亜鉛粒子の水性スラリー中で、無機化合物あるいは有機化合物を添加し中和するなどして被覆することができる。また、有機化合物を被覆するには別の方法として、酸化亜鉛粒子に有機化合物を添加してミキサーで乾式処理を行い、熱処理を施すなどして被覆することもできる。
The zinc oxide particles of the present invention may be provided with a coating layer of an oxide such as silicon, titanium, aluminum, zirconium, tin or an inorganic compound such as a phosphate thereof, if necessary, on the surface of the particles. One of these inorganic compounds may be used, or two or more thereof may be laminated or mixed. Further, for the purpose of imparting dispersibility to a solvent, a paint, plastics or the like, an organic compound may be coated, or both the inorganic compound and the organic compound may be coated. Examples of the organic compound include (1) an organosilicon compound ((a) an organopolysiloxane (dimethylpolysiloxane, methylhydrogenpolysiloxane, methylmethoxypolysiloxane, methylphenylpolysiloxane, dimethylpolysiloxanediol, and dimethylpolysiloxanediol). (B) organosilanes (amino silane, epoxy silane, methacryl silane, vinyl silane, mercapto silane, chloroalkyl silane, alkyl silane, fluoroalkyl silane, etc. or their hydrolysis products) , (C) organosilazanes (hexamethylsilazane, hexamethylcyclotrisilazane, etc.), etc.),
(2) organometallic compounds ((a) organotitanium compounds (aminoalkoxytitanium, phosphate titanium, carboxylate titanium, sulfonate titanium, titanium chelate, phosphite titanium complex, etc.), (b) organoaluminum Compounds (such as aluminum chelates), (c) organic zirconium compounds (such as zirconium carboxylate and zirconium chelates), etc.),
(3) polyols (trimethylolpropane, trimethylolethane, pentaerythritol, etc.),
(4) alkanolamines (monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, etc.) or derivatives thereof (acetate, oxalate, tartrate, formate, benzoate) Organic acid salts, etc.),
(5) higher fatty acids (stearic acid, lauric acid, oleic acid, etc.) or metal salts thereof (aluminum salt, zinc salt, magnesium salt, calcium salt, barium salt, etc.),
(6) Higher hydrocarbons (paraffin wax, polyethylene wax, etc.) or derivatives thereof (perfluorinated compounds, etc.). One of these organic compounds may be used, or two or more thereof may be laminated or mixed. The coating amount of the inorganic compound and the organic compound is preferably in the range of 0.1 to 50% by mass, more preferably 0.1 to 30% by mass, based on the zinc oxide particles.
In order to coat the inorganic compound or the organic compound on the surface of the zinc oxide particles, the inorganic compound or the organic compound may be added to the aqueous slurry of the zinc oxide particles to neutralize the coating. As another method for coating the organic compound, the zinc oxide particles can be coated by adding the organic compound, performing a dry treatment with a mixer, and performing a heat treatment.
本発明の角丸多面体形状酸化亜鉛粒子や他のフィラーとの混合物（以降、総称して酸化亜鉛粒子と記載する）は、その他の成分と混合して、化粧料、インキ、塗料、プラスチック等に配合することができる。 The mixture of the rounded polyhedral shaped zinc oxide particles of the present invention and other fillers (hereinafter collectively referred to as zinc oxide particles) is mixed with other components to form cosmetics, inks, paints, plastics and the like. Can be blended.
上記化粧料としては特に限定されず、本発明の酸化亜鉛粒子の粉体を紫外線遮蔽材、白色顔料、充填材等として、化粧品原料と混合することによって、日焼け止め化粧料、ファンデーション等の基礎化粧料、口紅等のポイントメイク化粧料等を得ることができる。本発明の酸化亜鉛粒子は化粧品に使用した場合に肌へのすべり感がよくなり好適である。 The cosmetic is not particularly limited, and the powder of the zinc oxide particles of the present invention is mixed with cosmetic raw materials as an ultraviolet ray shielding material, a white pigment, a filler, and the like, so that basic cosmetics such as sunscreen cosmetics and foundations can be obtained. Point makeup cosmetics such as cosmetics and lipstick. The zinc oxide particles of the present invention are suitable for use in cosmetics because they have a good feeling of slipping on the skin.
本発明の化粧料には、前記酸化亜鉛粒子以外に、通常化粧料に用いられる公知の成分、例えば、（１）溶媒（水、低級アルコール類等）、（２）油剤（高級脂肪酸類、高級アルコール類、オルガノポリシロキサン類（シリコーンオイル）、炭化水素類、油脂類等）、（３）界面活性剤（アニオン性、カチオン性、両性、非イオン性等）、（４）保湿剤（グリセリン類、グリコール等のポリオール系、ピロリドンカルボン酸類等の非ポリオール系等）（５）有機紫外線吸収剤（ベンゾフェノン誘導体、パラアミノ安息香酸誘導体、サリチル酸誘導体等）、（６）酸化防止剤（フェノール系、有機酸又はその塩、酸アミド系、リン酸系等）、（７）増粘剤、（８）香料、（９）着色剤（顔料、色素、染料等）、（１０）生理活性成分（ビタミン類、ホルモン類、アミノ酸類等）、（１１）抗菌剤等が配合されていてもよい。化粧料の様態は、固形状、液状、ジェル状等特に制限なく、液状やジェル状の場合、その分散形態も油中水型エマルジョン、水中油型エマルジョン、油型等のいずれでもよい。化粧料中の酸化亜鉛粒子の配合量は、０．１〜５０質量％の範囲が好ましい。 In the cosmetic of the present invention, in addition to the zinc oxide particles, known components usually used in cosmetics such as (1) solvents (water, lower alcohols, etc.), (2) oils (higher fatty acids, higher fatty acids, etc.) Alcohols, organopolysiloxanes (silicone oil), hydrocarbons, oils and fats), (3) surfactants (anionic, cationic, amphoteric, nonionic, etc.), (4) humectants (glycerins) , Glycols, etc., non-polyols such as pyrrolidone carboxylic acids, etc.) (5) Organic UV absorbers (benzophenone derivatives, paraaminobenzoic acid derivatives, salicylic acid derivatives, etc.), (6) Antioxidants (phenolic, organic acids) Or salts thereof, acid amides, phosphoric acids, etc.), (7) thickeners, (8) fragrances, (9) coloring agents (pigments, pigments, dyes, etc.), (10) bioactive ingredients (vitamins) Hormones, amino acids, etc.), (11) an antibacterial agent or the like may be blended. The form of the cosmetic is not particularly limited, such as solid, liquid, and gel. In the case of liquid or gel, the dispersion form may be any of a water-in-oil emulsion, an oil-in-water emulsion, and an oil form. The blending amount of the zinc oxide particles in the cosmetic is preferably in the range of 0.1 to 50% by mass.
本発明の放熱性組成物は、上記の酸化亜鉛粒子を放熱フィラーとして含有したものであり、樹脂組成物、グリース組成物、塗料組成物などが挙げられる。また、それらを用いて形成するシート、ゲル、エラストマー、プラスチックなどであってもよい。 The heat dissipating composition of the present invention contains the above zinc oxide particles as a heat dissipating filler, and includes a resin composition, a grease composition, a coating composition and the like. Further, sheets, gels, elastomers, plastics, and the like formed using them may be used.
本発明の樹脂組成物は、前記酸化亜鉛粒子と樹脂成分を少なくとも含む組成物であり、前記放熱性組成物に包含される放熱性樹脂組成物も含む。樹脂組成物に使用する樹脂は、熱可塑性樹脂であっても熱硬化性樹脂であってもよく、エポキシ樹脂、アクリル樹脂、フェノール樹脂、ポリフェニレンサルファイド（ＰＰＳ）樹脂、ポリエステル系樹脂、ポリアミド、ポリイミド、ポリスチレン、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリ塩化ビニリデン、フッ素樹脂、ポリメタクリル酸メチル、エチレン・アクリル酸エチル共重合体（ＥＥＡ）樹脂、ポリカーボネート、ポリウレタン、ポリアセタール、ポリフェニレンエーテル、ポリエーテルイミド、アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ）樹脂、液晶樹脂（ＬＣＰ）、シリコーン樹脂等の樹脂を挙げることができる。 The resin composition of the present invention is a composition containing at least the zinc oxide particles and a resin component, and also includes a heat radiation resin composition included in the heat radiation composition. The resin used for the resin composition may be a thermoplastic resin or a thermosetting resin, and may be an epoxy resin, an acrylic resin, a phenol resin, a polyphenylene sulfide (PPS) resin, a polyester resin, a polyamide, a polyimide, Polystyrene, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, fluororesin, polymethyl methacrylate, ethylene / ethyl acrylate copolymer (EEA) resin, polycarbonate, polyurethane, polyacetal, polyphenylene ether, polyetherimide, acrylonitrile Resins such as butadiene-styrene copolymer (ABS) resin, liquid crystal resin (LCP), and silicone resin can be used.
本発明の樹脂組成物は、（１）熱可塑性樹脂と上記酸化亜鉛粒子とを溶融状態で混練することによって得られた熱成型用の樹脂組成物（２）熱硬化性樹脂と上記酸化亜鉛粒子とを混練後、加熱硬化させることによって得られた樹脂組成物、等のいずれの形態であってもよい。 The resin composition of the present invention comprises (1) a resin composition for thermoforming obtained by kneading a thermoplastic resin and the above zinc oxide particles in a molten state, (2) a thermosetting resin and the above zinc oxide particles. May be in any form such as a resin composition obtained by kneading and heat-curing.
本発明の樹脂組成物を放熱性樹脂組成物として用いる場合、組成物中の上記酸化亜鉛粒子の配合量は、目的とする熱伝導率や樹脂組成物の硬度等、樹脂組成物の性能に合わせて任意に決定することができる。上記酸化亜鉛粒子の放熱性能を充分に発現させるためには、放熱性樹脂組成物中の固形分全量に対して１体積％以上含有することが好ましい。上記配合量は必要とされる放熱性能に応じて配合量を調整して使用することができ、より高い放熱性が要求される用途においては、５体積％以上がより好ましく、１０体積％以上が更に好ましい。このようにして、放熱性樹脂組成物の熱伝導率を好ましくは０．５Ｗ／ｍ・Ｋ以上とすることができ、より好ましくは２．０Ｗ／ｍ・Ｋ以上とすることができる。具体的には、上記酸化亜鉛粒子５０体積％：エポキシ樹脂５０体積％で配合した液状の樹脂組成物において、粘度を実用領域である１０〜５００Ｐａ・ｓとすることができ、これを固化した固形物状の樹脂組成物において、熱伝導率を２．５Ｗ／ｍ・Ｋ以上とすることができる。 When the resin composition of the present invention is used as a heat-radiating resin composition, the amount of the zinc oxide particles in the composition depends on the performance of the resin composition, such as the intended thermal conductivity and the hardness of the resin composition. Can be determined arbitrarily. In order to sufficiently exhibit the heat dissipation performance of the zinc oxide particles, it is preferable that the zinc oxide particles be contained in an amount of 1% by volume or more based on the total solid content in the heat dissipation resin composition. The above-mentioned compounding amount can be used by adjusting the compounding amount according to the required heat radiation performance. In applications where higher heat radiation is required, 5 vol% or more is more preferable, and 10 vol% or more is preferable. More preferred. Thus, the thermal conductivity of the heat-dissipating resin composition can be preferably 0.5 W / m · K or more, and more preferably 2.0 W / m · K or more. Specifically, in a liquid resin composition blended with 50% by volume of the zinc oxide particles and 50% by volume of the epoxy resin, the viscosity can be set to a practical range of 10 to 500 Pa · s, and the solidified solid is obtained. In the physical resin composition, the thermal conductivity can be 2.5 W / m · K or more.
本発明の樹脂組成物は、用途によって樹脂成分を自由に選択することができる。例えば、熱源と放熱板の間に装着し密着させる場合には、エポキシ樹脂やシリコーン樹脂、アクリル樹脂のような接着性が高く硬度の低い、かつ、耐熱性の高い樹脂を選択すればよい。 In the resin composition of the present invention, the resin component can be freely selected depending on the application. For example, when a heat source and a heat radiating plate are attached and adhered to each other, a resin having high adhesiveness, low hardness, and high heat resistance, such as an epoxy resin, a silicone resin, or an acrylic resin, may be selected.
本発明の樹脂組成物が熱成型用の樹脂組成物である場合、熱可塑性樹脂と上記酸化亜鉛粒子を、例えば、スクリュー型二軸押出機を用いた溶融混練によって、樹脂組成物をペレット化し、その後射出成型等の任意の成形方法によって所望の形状に成型する方法等によって製造することができる。 When the resin composition of the present invention is a resin composition for thermoforming, the thermoplastic resin and the zinc oxide particles, for example, by melt-kneading using a screw-type twin-screw extruder, to pelletize the resin composition, Thereafter, it can be manufactured by a method of molding into a desired shape by any molding method such as injection molding.
本発明の樹脂組成物が熱硬化性樹脂と上記酸化亜鉛粒子とを混練後、加熱硬化させることによって得られた樹脂組成物である場合、例えば、加圧成形等によって成形するものであることが好ましい。このような樹脂組成物の製造方法は、特に限定されないが、例えば、樹脂組成物をトランスファー成型により成型し、製造することができる。 When the resin composition of the present invention is a resin composition obtained by kneading the thermosetting resin and the zinc oxide particles and then heating and curing, for example, the resin composition may be molded by pressure molding or the like. preferable. The method for producing such a resin composition is not particularly limited. For example, the resin composition can be produced by molding a resin composition by transfer molding.
本発明の放熱性樹脂組成物の用途は、電子部品の放熱部材、熱伝導性充填剤、温度測定用等の絶縁性充填剤等がある。例えば、本発明の放熱性樹脂組成物は、ＭＰＵ、パワートランジスタ、トランス等の発熱性電子部品からの熱を放熱フィンや放熱ファン等の放熱部品に伝熱させるために使用することができ、発熱性電子部品と放熱部品の間に挟み込まれて使用することができる。これによって、発熱性電子部品と放熱部品間の伝熱が良好となり、長期的に発熱性電子部品の誤作動を軽減させることができる。ヒートパイプとヒートシンクの接続や、種々の発熱体の組込まれたモジュールとヒートシンクとの接続に好適に用いることもできる。 Uses of the heat-radiating resin composition of the present invention include heat-radiating members for electronic components, heat-conductive fillers, insulating fillers for temperature measurement and the like. For example, the heat dissipating resin composition of the present invention can be used to transfer heat from heat generating electronic components such as MPUs, power transistors, and transformers to heat dissipating components such as heat dissipating fins and heat dissipating fans. It can be used by being sandwiched between a conductive electronic component and a heat dissipation component. As a result, the heat transfer between the heat-generating electronic component and the heat radiating component is improved, and malfunction of the heat-generating electronic component can be reduced in a long term. It can also be suitably used for connection between a heat pipe and a heat sink, and connection between a module incorporating various heating elements and a heat sink.
本発明の放熱性組成物には、鉱油又は合成油を含有する基油と上記酸化亜鉛粒子が混合された放熱性樹脂組成物である放熱性グリースが包含される。 The heat-dissipating composition of the present invention includes a heat-dissipating grease which is a heat-dissipating resin composition in which a base oil containing a mineral oil or a synthetic oil and the above zinc oxide particles are mixed.
本発明の放熱性グリース中の上記酸化亜鉛粒子の配合量は、目的とする熱伝導率に合わせて任意に決定する事ができる。上記酸化亜鉛粒子の放熱性能を充分に発現させるためには、放熱性グリース中の全量に対して１体積％以上含有する事が好ましい。上記配合量は必要とされる放熱性能に応じて配合量を調整して使用することができ、より高い放熱性が要求される用途においては、５体積％以上がより好ましく、１０体積％以上が更に好ましい。 The amount of the zinc oxide particles in the heat-dissipating grease of the present invention can be arbitrarily determined according to the intended thermal conductivity. In order to sufficiently exhibit the heat dissipation performance of the zinc oxide particles, the zinc oxide particles preferably contain 1% by volume or more based on the total amount in the heat dissipation grease. The above-mentioned compounding amount can be used by adjusting the compounding amount according to the required heat radiation performance. In applications where higher heat radiation is required, 5 vol% or more is more preferable, and 10 vol% or more is preferable. More preferred.
上記基油は、鉱油、合成油、シリコーンオイル、フッ素系炭化水素油等の各種油性材料を１種又は２種以上組み合わせて使用することができる。合成油としては特に炭化水素油がよい。合成油としてα−オレフィン、ジエステル、ポリオールエステル、トリメリット酸エステル、ポリフェニルエーテル、アルキルフェニルエーテルなどが使用できる。 As the base oil, various oily materials such as mineral oil, synthetic oil, silicone oil, and fluorocarbon oil can be used alone or in combination of two or more. Hydrocarbon oils are particularly preferred as synthetic oils. As synthetic oils, α-olefins, diesters, polyol esters, trimellitic esters, polyphenyl ethers, alkyl phenyl ethers and the like can be used.
本発明の放熱性グリースには、必要に応じて界面活性剤を添加してもよい。上記界面活性剤としては、非イオン系界面活性剤が好ましい。非イオン系界面活性剤の配合により、高熱伝導率化を図ることができる。 A surfactant may be added to the heat radiation grease of the present invention as needed. As the above surfactant, a nonionic surfactant is preferable. High thermal conductivity can be achieved by blending the nonionic surfactant.
非イオン系界面活性剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアルキルナフチルエーテル、ポリオキシエチレン化ヒマシ油、ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレンアルキルアミド、ポリオキシエチレン−ポリオキシプロピレングリコール、ポリオキシエチレン−ポリオキシプロピレングリコールエチレンジアミン、デカグリセリン脂肪酸エステル、ポリオキシエチレンモノ脂肪酸エステル、ポリオキシエチレンジ脂肪酸エステル、ポリオキシエチレンプロピレングリコール脂肪酸エステル、ポリオキシエチレンソルビタンモノ脂肪酸エステル、ポリオキシエチレンソルビタントリ脂肪酸エステル、エチレングリコールモノ脂肪酸エステル、ジエチレングリコールモノ脂肪酸エステル、プロピレングリコールモノ脂肪酸エステル、グリセリンモノ脂肪酸エステル、ペンタエリトリットモノ脂肪酸エステル、ソルビタンモノ脂肪酸エステル、ソルビタンセスキ脂肪酸エステル、ソルビタントリ脂肪酸エステルが挙げられる。 Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl naphthyl ether, polyoxyethylene castor oil, polyoxyethylene hardened castor oil, polyoxyethylene alkyl amide, and polyoxyethylene alkyl amide. Oxyethylene-polyoxypropylene glycol, polyoxyethylene-polyoxypropylene glycol ethylenediamine, decaglycerin fatty acid ester, polyoxyethylene monofatty acid ester, polyoxyethylene difatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene sorbitan mono Fatty acid ester, polyoxyethylene sorbitan trifatty acid ester, ethylene glycol monofatty acid ester, die Glycol mono fatty acid esters, propylene glycol mono fatty acid esters, glycerol mono-fatty acid esters, pentaerythritol fatty acid monoesters, sorbitan mono fatty acid esters, Sorubitansesuki fatty esters, sorbitan tri fatty acid ester.
非イオン系界面活性剤の添加の効果は、上記酸化亜鉛粒子の種類、配合量、及び親水性と親油性のバランスを示すＨＬＢ（親水親油バランス）によって異なる。また、高放熱性グリース等の電気絶縁性や電気抵抗の低下を重視しない用途では、アニオン系界面活性剤、カチオン系界面活性剤、両性界面活性剤を使用することができる。 The effect of the addition of the nonionic surfactant differs depending on the type and blending amount of the zinc oxide particles and the HLB (hydrophilic-lipophilic balance) showing the balance between hydrophilicity and lipophilicity. In addition, in applications in which reduction in electrical insulation and electrical resistance is not important, such as high heat radiation grease, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used.
本発明の放熱性グリースは、前述した成分をドウミキサー（ニーダー）、ゲートミキサー、プラネタリーミキサーなどの混合機器を用いて混合することによって調製することができる。 The heat-dissipating grease of the present invention can be prepared by mixing the above components using a mixing device such as a dough mixer (kneader), a gate mixer, a planetary mixer, or the like.
本発明の放熱性グリースは、発熱体や放熱体に塗布することによって使用される。発熱体としては、例えば、一般の電源；電源用パワートランジスタ、パワーモジュール、サーミスタ、熱電対、温度センサなどの電子機器；ＬＳＩ、ＣＰＵ等の集積回路素子などの発熱性電子部品などが挙げられる。放熱体としては、例えば、ヒートスプレッダ、ヒートシンク等の放熱部品；ヒートパイプ、放熱板などが挙げられる。塗布は、例えば、スクリーンプリントによって行うことができる。スクリーンプリントは、例えば、メタルマスクもしくはスクリーンメッシュを用いて行うことができる。前記放熱性グリースを発熱体及び放熱体の間に介在させて塗布することにより、上記発熱体から上記放熱体へ効率よく熱を伝導させることができるので、上記発熱体から効果的に熱を取り除くことができる。 The heat-dissipating grease of the present invention is used by applying it to a heating element or a heat-dissipating element. Examples of the heating element include a general power supply; electronic equipment such as a power transistor for power supply, a power module, a thermistor, a thermocouple, and a temperature sensor; and heat-generating electronic components such as an integrated circuit element such as an LSI and a CPU. Examples of the radiator include a radiator such as a heat spreader and a heat sink; a heat pipe and a radiator plate. The application can be performed, for example, by screen printing. Screen printing can be performed using, for example, a metal mask or a screen mesh. By applying the heat dissipating grease between the heat generating element and the heat dissipating element, heat can be efficiently conducted from the heat generating element to the heat dissipating element, so that the heat is effectively removed from the heat generating element. be able to.
本発明の塗料組成物は、前記酸化亜鉛粒子が樹脂溶液又は分散液中に分散された樹脂組成物である塗料組成物であり、前記放熱性組成物に包含される放熱性樹脂組成物も含む。この場合、使用する樹脂は硬化性を有するものであっても、硬化性を有さないものであってもよい。上記樹脂として具体的には、上述した樹脂組成物において使用することができる樹脂として例示した樹脂を挙げることができる。塗料は、有機溶剤を含有する溶剤系のものであっても、水中に樹脂が溶解又は分散した水系のものであってもよい。 The coating composition of the present invention is a coating composition in which the zinc oxide particles are a resin composition dispersed in a resin solution or dispersion, and also includes a heat-radiating resin composition included in the heat-radiating composition. . In this case, the resin used may be curable or non-curable. Specific examples of the resin include the resins exemplified as the resins that can be used in the resin composition described above. The paint may be a solvent-based paint containing an organic solvent or an aqueous paint in which a resin is dissolved or dispersed in water.
上記塗料の製造方法は、特に限定されないが、例えば、ディスパーやビーズミル等を使用し、必要とする原料及び溶剤を混合・分散することによって製造することができる。 The method for producing the paint is not particularly limited. For example, the paint can be produced by using a disper or a bead mill and mixing and dispersing necessary raw materials and a solvent.
本発明の塗料組成物を放熱性塗料組成物として用いる場合、組成物中の上記酸化亜鉛粒子の配合量は、目的とする熱伝導率に合わせて任意に決定する事ができる。上記酸化亜鉛粒子の放熱性能を充分に発現させるためには、塗料組成物全量に対して１体積％以上含有する事が好ましい。上記配合量は必要とされる放熱性能に応じて配合量を調整して使用することができ、より高い放熱性が要求される用途においては、５体積％以上がより好ましく、１０体積％以上が更に好ましい。 When the coating composition of the present invention is used as a heat-radiating coating composition, the amount of the zinc oxide particles in the composition can be arbitrarily determined according to the intended thermal conductivity. In order to sufficiently exhibit the heat radiation performance of the zinc oxide particles, the zinc oxide particles preferably contain 1% by volume or more based on the total amount of the coating composition. The above-mentioned compounding amount can be used by adjusting the compounding amount according to the required heat radiation performance. In applications where higher heat radiation is required, 5 vol% or more is more preferable, and 10 vol% or more is preferable. More preferred.
本発明の放熱性塗料組成物は、前述の放熱性樹脂組成物の項に記載した用途に用いることができる。その他、建築物の外壁、建材や、ボイラー等の熱を発する産業設備、家電製品等にも用いることができる。 The heat dissipation coating composition of the present invention can be used for the applications described in the section of the heat dissipation resin composition described above. In addition, it can also be used for the outer walls of buildings, building materials, industrial equipment that generates heat, such as boilers, and household electrical appliances.
前記の本発明のすべての放熱性組成物は、本発明の酸化亜鉛粒子以外の他の放熱フィラーを含有してもよい。他の放熱フィラーとしては特に限定されず、公知の任意のものを使用することができる。例えば、酸化亜鉛、酸化マグネシウム、酸化チタン、酸化アルミニウム、酸化ジルコニウム等の金属酸化物、窒化アルミニウム、窒化ホウ素、炭化ケイ素、窒化ケイ素、窒化チタン、金属シリコン、金属粒子、炭素化合物（ダイヤモンド、グラファイト、グラフェン、カーボンナノチューブ等）等を挙げることができる。本発明の酸化亜鉛粒子と組み合わせる場合は、他の放熱フィラーは一種類に限定されることはなく、複数種類の放熱フィラーを併用してもよい。 All the heat radiation compositions of the present invention described above may contain a heat radiation filler other than the zinc oxide particles of the present invention. The other heat radiation filler is not particularly limited, and any known heat radiation filler can be used. For example, metal oxides such as zinc oxide, magnesium oxide, titanium oxide, aluminum oxide, and zirconium oxide, aluminum nitride, boron nitride, silicon carbide, silicon nitride, titanium nitride, metal silicon, metal particles, and carbon compounds (diamond, graphite, Graphene, carbon nanotube, etc.). When combined with the zinc oxide particles of the present invention, the other heat dissipating filler is not limited to one kind, and a plurality of kinds of heat dissipating fillers may be used in combination.
前記他の放熱フィラーとして、粒子サイズの異なる酸化亜鉛粒子や、粒子サイズの異なる他物質の放熱フィラーを用いてもよい。本発明の角丸多面体形状酸化亜鉛粒子を粒子径の大きい主放熱フィラーとして用いる場合には、メジアン径Ｒは５〜１００μｍとするのが好ましく、５〜４０μｍとするとより好ましい。主放熱フィラーとして角丸多面体形状酸化亜鉛粒子を使用すると、樹脂等の媒体への充填性が良好（高い充填率での配合が可能）であり、放熱性組成物中に熱伝導パスが形成され易いため、熱伝導は生じ易く、良好に放熱することができる。また、組成物に配合したときに、粒子の表面エネルギーが小さいため、樹脂等になじみ易くなる結果、組成物の流動性を確保できる。特に、メジアン径がＲ／４０〜Ｒ／２（μｍ）の範囲の粒子サイズの小さい副放熱フィラーを本発明の酸化亜鉛粒子と組成物中に配合して用いると、本発明の多面体形状酸化亜鉛粒子同士の間の空隙を埋めて組成物中のフィラー充填率を高めることができるとともに、潤滑剤様に機能して組成物の流動性を高めることができる。その他の放熱フィラーには特に制限は無く任意の材料を用いることができる。中でも金属酸化物が好ましく、酸化亜鉛及び又は酸化アルミニウムがより好ましい。本発明の酸化亜鉛粒子とその他の放熱フィラーの配合比率には特に制限はなく適宜調整すればよい。体積比で７：３〜９：１の範囲が好適である。その他の放熱フィラーの形状には特に限定はなく、球状、粒状、立方体状、棒状、六角板状、鱗片状、不定形状等を挙げることができる。当該その他の放熱フィラーにも無機化合物や有機化合物を被覆してもよい。 As the other heat radiation filler, zinc oxide particles having different particle sizes or heat radiation fillers of other materials having different particle sizes may be used. When the rounded polyhedral zinc oxide particles of the present invention are used as the main heat-radiating filler having a large particle diameter, the median diameter R is preferably 5 to 100 μm, and more preferably 5 to 40 μm. When the rounded polyhedral zinc oxide particles are used as the main heat-radiating filler, the filling property of the resin or other medium into the medium is good (can be blended at a high filling rate), and a heat-conducting path is formed in the heat-radiating composition. Therefore, heat conduction easily occurs, and heat can be radiated well. Further, when incorporated into the composition, the surface energy of the particles is small, so that the particles easily become compatible with a resin or the like, so that the fluidity of the composition can be ensured. In particular, when a secondary heat-radiating filler having a small median diameter in the range of R / 40 to R / 2 (μm) is blended with the zinc oxide particles of the present invention and the composition, the polyhedral zinc oxide of the present invention is used. The filler between the particles can be filled by filling the voids between the particles, and the composition can function as a lubricant to increase the fluidity of the composition. The other heat radiation filler is not particularly limited, and any material can be used. Among them, metal oxides are preferable, and zinc oxide and / or aluminum oxide are more preferable. The mixing ratio of the zinc oxide particles of the present invention and other heat-radiating fillers is not particularly limited, and may be appropriately adjusted. A range of 7: 3 to 9: 1 by volume ratio is preferred. The shape of the other heat radiation filler is not particularly limited, and examples thereof include a spherical shape, a granular shape, a cubic shape, a rod shape, a hexagonal plate shape, a scale shape, and an irregular shape. The other heat dissipation filler may be coated with an inorganic compound or an organic compound.
本発明の角丸多面体形状酸化亜鉛粒子を粒子径の小さい副放熱フィラーとして用いる場合には、そのメジアン径Ｒは１〜１０μｍとするのが好ましい。副放熱フィラーとして角丸多面体形状酸化亜鉛粒子を使用すると、組成物に配合したときに、粒子の表面エネルギーが小さいため、樹脂等になじみ易くなる結果、組成物の流動性を確保できる。この場合、大粒径の主放熱フィラーの粒子径は、副放熱フィラーのメジアン径Ｒに対して２Ｒ〜４０Ｒ（μｍ）の範囲とすると好ましい。本発明の角丸多面体形状酸化亜鉛粒子を副放熱フィラーとして使用することで、主放熱フィラーの隙間を埋めることができる。ひいては、放熱性組成物への充填性を高めることができ、熱伝導性を向上させることができる。加えて、主放熱フィラーの隙間に副放熱フィラーが介在することで、これらが潤滑剤の役割を果たし、放熱性組成物の流動性をより維持し易くすることができる。大粒径の主放熱フィラーと本発明の酸化亜鉛粒子との配合比率には特に制限がなく、適宜調整することができ、例えば、体積比で７：３〜９：１の範囲が好適である。 When the rounded polyhedral shaped zinc oxide particles of the present invention are used as a sub-radiating filler having a small particle diameter, the median diameter R is preferably 1 to 10 μm. When the rounded polyhedral zinc oxide particles are used as the auxiliary heat-radiating filler, the surface energy of the particles is small when blended in the composition, so that the particles are easily adapted to a resin or the like, so that the fluidity of the composition can be secured. In this case, the particle diameter of the main heat radiation filler having a large particle diameter is preferably in the range of 2R to 40R (μm) with respect to the median diameter R of the sub heat radiation filler. By using the rounded polyhedral shaped zinc oxide particles of the present invention as the auxiliary heat radiating filler, the gap between the main heat radiating fillers can be filled. As a result, it is possible to enhance the filling property of the heat-dissipating composition and to improve the thermal conductivity. In addition, since the auxiliary heat radiating filler is interposed in the gap between the main heat radiating fillers, they function as a lubricant, and the fluidity of the heat radiating composition can be more easily maintained. There are no particular restrictions on the mixing ratio of the main heat-radiating filler having a large particle diameter and the zinc oxide particles of the present invention, and the mixing ratio can be appropriately adjusted. For example, a volume ratio of 7: 3 to 9: 1 is preferable. .
このようにして、メジアン径が異なる放熱フィラーを併用することにより、放熱性樹脂組成物の熱伝導率を好ましくは０．５Ｗ／ｍ・Ｋ以上とすることができ、より好ましくは２．５Ｗ／ｍ・Ｋ以上とすることができる。具体的には、上記酸化亜鉛粒子５０体積％以上で配合した液状の樹脂組成物において、粘度を実用領域である１０〜５００Ｐａ・ｓとすることができ、これを固化した固形物状の樹脂組成物において、熱伝導率を３．０Ｗ／ｍ・Ｋ以上とすることができる。 In this way, by using a heat-radiating filler having a different median diameter in combination, the thermal conductivity of the heat-radiating resin composition can be preferably 0.5 W / m · K or more, more preferably 2.5 W / m · K. m · K or more. Specifically, the viscosity of the liquid resin composition blended with 50% by volume or more of the zinc oxide particles can be set to a practical range of 10 to 500 Pa · s, and the solidified resin composition obtained by solidifying the viscosity is obtained. The object can have a thermal conductivity of 3.0 W / m · K or more.
以下、本発明を実施例に基づいて更に詳細に説明する。なお、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples. Note that the present invention is not limited to the following embodiments.
＜比較例１＞
硫酸亜鉛七水和物０．６モルとクエン酸三ナトリウム二水和物０．００２モルとを、５Ｌのビーカー中で７００ｍＬの純水に溶解した。この水溶液を撹拌機で撹拌しながら、この水溶液に室温で、１．５５モルのモノエタノールアミンを７００ｍＬの水に溶解させた水溶液を１０分間かけて添加し、６０分間保持した。その後水溶液を加熱して、９５℃まで昇温させた。水溶液の温度を９５℃に保持し、撹拌機で撹拌しながら、４時間の間熟成を行い、水溶液中に白色沈殿を得た。吸引ろ過によって上記白色沈殿を回収し、１５０℃、３時間乾燥し、試料ａを得た。Ｘ線回折パターンの測定の結果、試料ａは酸化亜鉛粒子であることが確認された。試料ａの走査電子顕微鏡写真を図１に示す。
<Comparative Example 1>
0.6 mol of zinc sulfate heptahydrate and 0.002 mol of trisodium citrate dihydrate were dissolved in 700 mL of pure water in a 5 L beaker. While stirring the aqueous solution with a stirrer, an aqueous solution in which 1.55 mol of monoethanolamine was dissolved in 700 mL of water was added to the aqueous solution at room temperature over 10 minutes, and the solution was maintained for 60 minutes. Thereafter, the aqueous solution was heated to 95 ° C. The temperature of the aqueous solution was maintained at 95 ° C., and aging was performed for 4 hours while stirring with a stirrer to obtain a white precipitate in the aqueous solution. The white precipitate was collected by suction filtration and dried at 150 ° C. for 3 hours to obtain a sample a. As a result of the measurement of the X-ray diffraction pattern, it was confirmed that the sample a was zinc oxide particles. FIG. 1 shows a scanning electron micrograph of the sample a.
＜比較例２＞
クエン酸三ナトリウム二水和物とモノエタノールアミンの添加量をそれぞれ、０．００６モルと１．８０モルに変更した以外は比較例１と同様にして試料ｂを得た。Ｘ線回折パターンの測定の結果、試料ｂは酸化亜鉛粒子であることが確認された。試料ｂの走査電子顕微鏡写真を図３に示す。
<Comparative Example 2>
Sample b was obtained in the same manner as in Comparative Example 1 except that the addition amounts of trisodium citrate dihydrate and monoethanolamine were changed to 0.006 mol and 1.80 mol, respectively. As a result of the measurement of the X-ray diffraction pattern, it was confirmed that the sample b was zinc oxide particles. FIG. 3 shows a scanning electron micrograph of the sample b.
＜比較例３＞
モノエタノールアミンの添加量を１．８０モルに変更した以外は比較例１と同様にして試料ｃを得た。Ｘ線回折パターンの測定の結果、試料ｃは酸化亜鉛粒子であることが確認された。試料ｃの走査電子顕微鏡写真を図５に示す。
<Comparative Example 3>
Sample c was obtained in the same manner as in Comparative Example 1, except that the amount of monoethanolamine added was changed to 1.80 mol. As a result of the measurement of the X-ray diffraction pattern, it was confirmed that Sample c was zinc oxide particles. FIG. 5 shows a scanning electron micrograph of Sample c.
＜比較例４＞
Ｚｎ４ＳＯ４（ＯＨ）６・５Ｈ２Ｏの組成式で表される層状亜鉛化合物８２ｇを１４００ｍＬの水に分散させた。そしてこの分散液を加熱して、９５℃まで昇温させた。昇温後は、水溶液の温度を９５℃に保持し、撹拌機で撹拌しながら、０．３１モルのモノエタノールアミンを１４０ｍＬの水に溶解させた水溶液を添加した。９５℃で８時間の間熟成を行い、水溶液中に白色沈殿を得た。上記白色沈殿を吸引ろ過によって回収し、１５０℃、３時間乾燥し、試料Ａを得た。Ｘ線回折パターンの測定の結果、試料ｄは酸化亜鉛粒子であることが確認された。試料ｄの走査電子顕微鏡写真を図７に示す。
<Comparative Example 4>
Zn 4 was SO 4 a (OH) 6 · 5H 2 O layered zinc compound 82g represented by the composition formula was dispersed in water 1400 mL. Then, the dispersion was heated to 95 ° C. After the temperature was raised, the temperature of the aqueous solution was maintained at 95 ° C., and an aqueous solution in which 0.31 mol of monoethanolamine was dissolved in 140 mL of water was added while stirring with a stirrer. Aging was performed at 95 ° C. for 8 hours to obtain a white precipitate in the aqueous solution. The white precipitate was collected by suction filtration and dried at 150 ° C. for 3 hours to obtain Sample A. As a result of measuring the X-ray diffraction pattern, it was confirmed that the sample d was zinc oxide particles. FIG. 7 shows a scanning electron micrograph of Sample d.
＜実施例１＞
試料ａを３Ｌビーカーに１００ｇ秤量し、 純水１Ｌを加えてスラリー化した。このスラリーを撹拌機で撹拌しながら室温下、酸化亜鉛のモル数に対して１０％相当の希硫酸（濃度２％）を１時間かけて添加した。溶液のｐＨは６〜８の範囲であった。酸添加後、生じた白色沈殿を吸引ろ過で回収後、乾燥して、７００℃で２時間焼成して、酸化亜鉛粒子（試料Ａ）を得た。試料Ａの走査電子顕微鏡写真を図２に示す。
<Example 1>
100 g of the sample a was weighed into a 3 L beaker, and 1 L of pure water was added to form a slurry. While stirring this slurry with a stirrer, dilute sulfuric acid (concentration: 2%) corresponding to 10% of the number of moles of zinc oxide was added over 1 hour at room temperature. The pH of the solution was in the range of 6-8. After the addition of the acid, the resulting white precipitate was collected by suction filtration, dried, and calcined at 700 ° C. for 2 hours to obtain zinc oxide particles (sample A). A scanning electron micrograph of Sample A is shown in FIG.
＜実施例２＞
試料ａに代えて試料ｂを用いた以外は実施例１と同様にして酸化亜鉛粒子（試料Ｂ）を得た。試料Ｂの走査電子顕微鏡写真を図４に示す。
<Example 2>
Zinc oxide particles (Sample B) were obtained in the same manner as in Example 1 except that Sample b was used instead of Sample a. A scanning electron micrograph of Sample B is shown in FIG.
＜実施例３＞
試料ａに代えて試料ｃを用いた以外は実施例１と同様にして酸化亜鉛粒子（試料Ｃ）を得た。試料Ｃの走査電子顕微鏡写真を図６に示す。
<Example 3>
Zinc oxide particles (Sample C) were obtained in the same manner as in Example 1 except that Sample c was used instead of Sample a. A scanning electron micrograph of Sample C is shown in FIG.
＜実施例４＞
試料ａに代えて試料ｄを用いた以外は実施例１と同様にして酸化亜鉛粒子（試料Ｄ）を得た。試料Ｄの走査電子顕微鏡写真を図８に示す。
<Example 4>
Zinc oxide particles (Sample D) were obtained in the same manner as in Example 1 except that Sample d was used instead of Sample a. A scanning electron micrograph of Sample D is shown in FIG.
試料Ａ〜Ｄ及び試料ａ〜ｄについて、レーザー回折／散乱式粒子径分布測定装置（堀場製作所社製 Ｐａｒｔｉｃａ ＬＡ−９５０Ｖ２）を用いてメジアン径Ｒを測定した。詳細には、ヘキサメタリン酸ナトリウムを０．２％溶解させた水溶液を分散媒とし、その中に各試料を混合し、装置内で循環・撹拌しながら、超音波を３分照射した後、粒度分布を測定し、粒度分布における頻度の累積が５０％となる粒子径をメジアン径Ｒとした。 For the samples A to D and the samples a to d, the median diameter R was measured using a laser diffraction / scattering type particle size distribution measuring device (Partica LA-950V2 manufactured by Horiba, Ltd.). In detail, an aqueous solution in which sodium hexametaphosphate is dissolved in 0.2% is used as a dispersion medium, each sample is mixed therein, and the mixture is circulated and stirred in the apparatus, irradiated with ultrasonic waves for 3 minutes, and then subjected to particle size distribution. Was measured, and the particle diameter at which the cumulative frequency in the particle size distribution became 50% was defined as the median diameter R.
また、試料Ａ〜Ｄ及び試料ａ、ｄについて、平均結晶子径ｒを求めた。また、求めたｒとメジアン径Ｒの比Ｒ／ｒを算出した。平均結晶子径ｒは、試料水平型多目的Ｘ線回折装置（Ｒｉｇａｋｕ社製 Ｕｌｔｉｍａ ＩＶ）を用いて測定した。詳細には、前記装置によって下記条件で各試料のＸ線回折パターンを測定し、その２θ＝３４°における回折ピーク（酸化亜鉛の（００２）面の回折ピーク）の半価幅の値を用いて、シェラーの式（式１）を用いて算出した。
（式１）・・・ｒ＝（Ｋ・λ）／βｃｏｓθ
ｒ：平均結晶子径（Å）
λ：Ｘ線の波長（ＣｕＫα線 １．５４１Å）
β：回折ピークの半価幅
θ：ブラッグ角
Ｋ：定数（＝０．９４）
（１） 光学系
（ア）入射スリット １°
（イ）長手制限スリット ２ｍｍ
（ウ）受光スリット１ １°
（エ）Ｋβフィルター あり
（オ）受光スリット ０．３ｍｍ
（２） 測定範囲：５〜５０ｄｅｇ
（３） 走査方法
（ア）スキャン速度 ８．０００ｄｅｇ／ｍｉｎ
（イ）ステップ幅 ０．０２００ｄｅｇ
In addition, the average crystallite diameter r of the samples A to D and the samples a and d was determined. Further, a ratio R / r between the obtained r and the median diameter R was calculated. The average crystallite diameter r was measured using a sample horizontal multipurpose X-ray diffractometer (Ultima IV manufactured by Rigaku). Specifically, the X-ray diffraction pattern of each sample was measured by the above-described apparatus under the following conditions, and the half-width value of the diffraction peak (the diffraction peak of the (002) plane of zinc oxide) at 2θ = 34 ° was used. , And Scherrer's equation (Equation 1).
(Equation 1): r = (K · λ) / βcosθ
r: average crystallite diameter (Å)
λ: X-ray wavelength (CuKα ray 1.541 °)
β: half width of diffraction peak θ: Bragg angle K: constant (= 0.94)
(1) Optical system (a) Incident slit 1 °
(A) Longitudinal limit slit 2mm
(C) Light receiving slit 11 1 °
(D) Kβ filter available (E) Light receiving slit 0.3mm
(2) Measurement range: 5 to 50 deg
(3) Scanning method (a) Scan speed 8.000 deg / min
(A) Step width 0.0200deg
また、試料Ａ〜Ｄ及び試料ａ〜ｄについて、走査電子顕微鏡写真から、２０個の粒子を用いて平均わたり径Ｌ、平均高さＨ、アスペクト比Ｈ／Ｌを求めた。 Further, with respect to Samples A to D and Samples a to d, an average diameter L, an average height H, and an aspect ratio H / L were obtained from 20 scanning particles using 20 particles.
また、試料Ａ、Ｄ及び試料ａ、ｄについてはタップ密度も測定した。タップ密度は、ＪＩＳ Ｒ １６３９−２に従い、各試料それぞれ５０ｇを１００ミリリットルのメスシリンダーにいれ、１００回タッピングして測定した。 The tap densities of the samples A and D and the samples a and d were also measured. The tap density was measured according to JIS R 1639-2 by placing 50 g of each sample in a 100 ml measuring cylinder and tapping 100 times.
以上の結果を表１に示す。 Table 1 shows the above results.
上述の実施前後の酸化亜鉛粒子の走査型電子顕微鏡（ＳＥＭ）写真の図１、２を対比して明らかなように、少量の希硫酸を断続的に添加することで、酸化亜鉛試料aの六角柱状形状を維持しながら、頂点や稜線が選択的に溶解され、丸みを帯びた形状になっていることが分かる。試料ｂ、ｃ、ｄと、処理後の試料Ｂ、Ｃ、Ｄの走査型電子顕微鏡（ＳＥＭ）写真からも同様のことが分かる。試料Ａに比べてアスペクト比が小さな試料Ｂ、大きな試料Ｃのどちらも頂点や稜線のみが選択的に溶解され、アスペクト比の大小に関わらず、丸み形状を付与できることが分かる。また、メジアン径が大きく、表面に錐台状や板状の凸部が存在する試料ｄにおいても、六角柱の頂点や稜線が曲面状になるとともに前記凸部が瘤状や鱗状となり、もとの多面体形状を維持しながら丸み形状を付与できることが分かる。試料Ａとａを対比すると、酸処理により六角柱状を角丸六角柱状とすることで、タップ密度が高くなることが確認できた。試料Ｄとｄの対比でも、同様にタップ密度が高くなることが確認できた。 As is clear from comparison with FIGS. 1 and 2 of the scanning electron microscope (SEM) photographs of the zinc oxide particles before and after the above-described implementation, the hexagonal shape of the zinc oxide sample a was obtained by intermittently adding a small amount of dilute sulfuric acid. It can be seen that the vertices and ridges are selectively melted while maintaining the columnar shape, resulting in a rounded shape. The same can be seen from the scanning electron microscope (SEM) photographs of the samples b, c, and d and the processed samples B, C, and D. It can be seen that, in both the sample B and the sample C having a smaller aspect ratio than the sample A, only the vertices and ridges are selectively dissolved, and a round shape can be imparted regardless of the magnitude of the aspect ratio. Further, even in the sample d having a large median diameter and a frustum-shaped or plate-shaped projection on the surface, the vertices and ridges of the hexagonal prism become curved and the projection becomes a bump or scale, and It can be seen that a rounded shape can be imparted while maintaining the polyhedral shape. Comparing Samples A and a, it was confirmed that the tap density was increased by changing the hexagonal column into a rounded hexagonal column by acid treatment. Also in comparison between Samples D and d, it was confirmed that the tap density was similarly increased.
＜前処理＞
上記試料Ａ〜Ｄ及び試料ａ〜ｄに対して０．５質量％のエポキシシラン（ＫＢＭ−４０３：信越化学社製）を添加し、ミキサーで乾式処理を行い、１５０℃で３時間熱処理して有機物被覆を施し、各前処理試料を得た。
<Pre-processing>
0.5 mass% of epoxysilane (KBM-403: manufactured by Shin-Etsu Chemical Co., Ltd.) is added to the samples A to D and the samples a to d, dry-processed by a mixer, and heat-treated at 150 ° C. for 3 hours. An organic coating was applied to obtain each pretreatment sample.
＜流動性評価＞
上記前処理を施した試料Ａ〜Ｃ、ａ〜ｃを用いて、次のようにして流動性評価用の樹脂組成物を作製した。先ず、樹脂（ｊＥＲ（登録商標）−８０７：ビスフェノールＦ型エポキシ樹脂、三菱化学社製）と、試料とをスクリュー瓶に秤量し、２０００ｒｐｍで３分間混練した。続いて、１０００ｒｐｍで１分間混練することで脱泡し、流動性測定用の樹脂組成物を作製した。尚、樹脂への試料の配合量（体積充填率）は４０％とした。
<Fluidity evaluation>
Using the samples A to C and a to c subjected to the above pretreatment, a resin composition for fluidity evaluation was prepared as follows. First, a resin (jER (registered trademark) -807: bisphenol F type epoxy resin, manufactured by Mitsubishi Chemical Corporation) and a sample were weighed into a screw bottle, and kneaded at 2000 rpm for 3 minutes. Subsequently, the mixture was defoamed by kneading at 1000 rpm for 1 minute to prepare a resin composition for measuring fluidity. The amount of the sample mixed with the resin (volume filling rate) was 40%.
これらの樹脂組成物について、粘度・粘弾性測定装置（ＨＡＡＫＥ ＲｈｅｏＳｔｒｅｓｓ ６０００、サーモサイエンティフィック社製）を用いて粘度測定を行った。測定条件は下記の通りで行い、コーン上に０．５ｍＬ程度の樹脂組成物を載せ、各回転数での粘度を測定した。流動性評価には、回転数が１ｒｐｍのときの粘度の値を使用し、比較を行った。結果を表２に示す。
・コーン：ＭＰ−２０, Ｃ２０/１ Ｈ
・測定温度：２５ ℃
・ギャップ：０．０５２ ｍｍ
・回転数：１, ２, ５, １０, ２０ ｒｐｍ
The viscosity of these resin compositions was measured using a viscosity / viscoelasticity measuring device (HAAKE RheoStress 6000, manufactured by Thermo Scientific). The measurement conditions were as follows, and about 0.5 mL of the resin composition was placed on the cone, and the viscosity at each rotation speed was measured. For the evaluation of the fluidity, the value of the viscosity at a rotation speed of 1 rpm was used for comparison. Table 2 shows the results.
・ Cone: MP-20, C20 / 1H
・ Measurement temperature: 25 ° C
・ Gap: 0.052 mm
・ Rotational speed: 1, 2, 5, 10, 20 rpm
アスペクト比によらず、酸処理により頂点や稜線に相当する部分が曲面状になったことで、粒子同士の干渉が抑制されて、１ｒｐｍのせん断応力かけたときの樹脂中での粘度が下がることが確認された。これらの結果から、アスペクト比によらず頂点や稜線を曲面状にすることで、流動性が向上することが分かる。 Irrespective of the aspect ratio, the parts corresponding to the vertices and ridges are curved by the acid treatment, so that the interference between particles is suppressed and the viscosity in the resin when a shear stress of 1 rpm is applied decreases. Was confirmed. From these results, it can be seen that the fluidity is improved by making the vertices and ridge lines curved regardless of the aspect ratio.
＜熱伝導性評価＞
上記前処理を施した試料を用いて、次のようにして熱伝導率測定用のサンプルを作製した。先ず、樹脂（ｊＥＲ（登録商標）−８０７）１００質量部及び試料１２３０質量部と共に、アミン硬化剤（Ｊｅｆｆａｍｉｎｅ（登録商標） ＥＤＲ−１４８、米国ハンツマン社製）２２質量部をスクリュー瓶に秤量し、上記粘度測定用の樹脂ペースト作製時と同様に混練、脱泡して、樹脂組成物を作製した。得られた樹脂組成物を加圧成型器に充填して、加圧させながら１５０℃に加温して固化し、熱伝導率測定用ペレットを作製した。樹脂への試料の配合量（体積充填率）は７０％である。
<Evaluation of thermal conductivity>
Using the sample subjected to the above pretreatment, a sample for measuring thermal conductivity was prepared as follows. First, along with 100 parts by mass of the resin (jER (registered trademark) -807) and 1230 parts by mass of a sample, 22 parts by mass of an amine curing agent (Jeffamine (registered trademark) EDR-148, manufactured by Huntsman, USA) were weighed into a screw bottle, Kneading and defoaming were performed in the same manner as in the preparation of the resin paste for viscosity measurement, to prepare a resin composition. The obtained resin composition was filled in a pressure molding machine, heated to 150 ° C. while being pressurized, and solidified to prepare a thermal conductivity measurement pellet. The blending amount (volume filling rate) of the sample in the resin is 70%.
上記熱伝導率測定用ペレットを用いて、以下の方法で熱伝導率を測定した。先ず、熱伝導率測定用ペレットを厚さ１ｍｍ程度まで研磨して評価用サンプルとした。評価用サンプルを、ＪＩＳ Ｒ １６１１に準拠し、熱拡散率評価装置（ＴＣ−７０００、アルバック理工社製）を用いて、雰囲気温度２５℃中、レーザーフラッシュ法にて熱拡散率を測定した。また、ＪＩＳ Ｋ ７１２３に準拠し、上記ペレットの比熱を、ＤＳＣ（示差走査熱量測定法 ＤＳＣ６２００ ＳＩＩ製）により測定した。更に、ＪＩＳ Ｋ ７１１２に準拠し、上記ペレットの比重を水中置換法により測定した。上述の方法で得られた熱拡散率、比熱、及び比重の値に基づいて、以下の式により熱伝導率を算出した。
熱伝導率＝熱拡散率×比熱×比重
結果を表３に示す。
Using the above-mentioned pellets for measuring thermal conductivity, the thermal conductivity was measured by the following method. First, the pellet for thermal conductivity measurement was polished to a thickness of about 1 mm to obtain a sample for evaluation. The thermal diffusivity of the evaluation sample was measured by a laser flash method in an atmosphere temperature of 25 ° C. using a thermal diffusivity evaluation apparatus (TC-7000, manufactured by ULVAC-RIKO) in accordance with JIS R 1611. The specific heat of the pellet was measured by DSC (differential scanning calorimetry DSC6200 SII) in accordance with JIS K 7123. Further, in accordance with JIS K7112, the specific gravity of the pellet was measured by an underwater displacement method. Based on the values of the thermal diffusivity, specific heat, and specific gravity obtained by the above method, the thermal conductivity was calculated by the following equation.
Table 3 shows the results of thermal conductivity = thermal diffusivity × specific heat × specific gravity.
角丸六角柱状の酸化亜鉛粒子はいずれも、６．６Ｗ／ｍＫ以上の高い熱伝導率を示すことが分かる。これは、酸処理で頂点や稜線に相当する部分が曲面状となったことにより、粒子同士が接触し易くなったことから熱伝導性が向上したものと考えられ、丸み形状を帯びさせることで熱伝導性を向上させることができることが分かった。特に、Ｈ／Ｌが０．５以上である、試料Ａ，Ｃ，Ｄでは酸処理前と比較して熱伝導率が向上しており、中でもＨ／Ｌが０．７〜１．５である試料Ａ，Ｄではその増加率が高くなることが確認できた。 It can be seen that each of the rounded hexagonal column-shaped zinc oxide particles has a high thermal conductivity of 6.6 W / mK or more. This is thought to be due to the fact that the parts corresponding to the vertices and ridges were curved by the acid treatment, so that the particles became easy to contact each other, and the thermal conductivity was improved. It has been found that the thermal conductivity can be improved. In particular, in Samples A, C, and D where the H / L is 0.5 or more, the thermal conductivity is improved as compared to before the acid treatment, and particularly, the H / L is 0.7 to 1.5. In samples A and D, the increase rate was confirmed to be high.
本発明の酸化亜鉛粒子は、充填性がよく、且つ、組成物として用いた場合に実用上充分な流動性を示す。そのため、化粧料、外用剤、塗料、グリース、繊維、樹脂組成物等に充填剤、白色顔料、熱伝導材料等として配合したり、あるいはセラミックス原料、導電材等に使用する際に、高濃度（高充填率）としても実用上充分な流動性を確保することができ、酸化亜鉛の特性を充分活用することができる。特に、本発明の酸化亜鉛粒子を放熱フィラーとして配合すると、実用上充分な流動性をもちつつ、熱伝導率の高い放熱性組成物が得ることができる。 The zinc oxide particles of the present invention have a good filling property and show practically sufficient fluidity when used as a composition. Therefore, when blended into cosmetics, external preparations, paints, greases, fibers, resin compositions, etc. as fillers, white pigments, heat conductive materials, etc., or when used in ceramic raw materials, conductive materials, etc., high concentrations ( Even at a high filling ratio), practically sufficient fluidity can be secured, and the properties of zinc oxide can be fully utilized. In particular, when the zinc oxide particles of the present invention are compounded as a heat-radiating filler, a heat-radiating composition having high thermal conductivity and having sufficient fluidity for practical use can be obtained.
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