TWI814778B - Composite particles, powders, resin compositions and molded bodies - Google Patents
Composite particles, powders, resin compositions and molded bodies Download PDFInfo
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- TWI814778B TWI814778B TW108104593A TW108104593A TWI814778B TW I814778 B TWI814778 B TW I814778B TW 108104593 A TW108104593 A TW 108104593A TW 108104593 A TW108104593 A TW 108104593A TW I814778 B TWI814778 B TW I814778B
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- particles
- ferrite
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
- H01F1/36—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites in the form of particles
- H01F1/37—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites in the form of particles in a bonding agent
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Soft Magnetic Materials (AREA)
- Compounds Of Iron (AREA)
Abstract
本發明提供一種具備由Mn鐵氧體所構成之母粒子、和包含選自由Au、Ag、Pt、Ni及Pd所組成的群組中至少1種的材料所構成之披覆層的複合粒子、一種包含複數個上述複合粒子的粉末、一種包含上述粉末、和樹脂材料的樹脂組合物、以及一種使用包含上述粉末、和樹脂材料之材料所製造而成的成形體。The present invention provides a composite particle including a mother particle made of Mn ferrite and a coating layer made of at least one material selected from the group consisting of Au, Ag, Pt, Ni and Pd. A powder containing a plurality of the above-mentioned composite particles, a resin composition containing the above-mentioned powder and a resin material, and a molded body produced using a material containing the above-mentioned powder and a resin material.
Description
本發明係有關於複合粒子、粉末、樹脂組合物及成形體。The present invention relates to composite particles, powders, resin compositions and molded articles.
近年來隨著電子設備的小型化、輕量化（例如，智慧型手機等），對於安裝在電子設備中的電子部件（包含模組、基板等），在小型化的同時以高密度組裝於電子設備的殼體內部並以高頻率運作的情況也增加了。In recent years, with the miniaturization and weight reduction of electronic equipment (for example, smartphones, etc.), the electronic components (including modules, substrates, etc.) installed in the electronic equipment have to be miniaturized and assembled in high density at the same time. There is also an increase in the number of devices that are inside the casing and operating at high frequencies.
由於以高密度組裝於殼體內，電子部件之間的距離縮短，變得容易受到從電子電路產生的電磁波雜訊（noise）的影響，而且容易變成從電子部件產生的熱能難以散出之結構，因此需要可以在較高溫度下操作的電子部件和能夠抑制電磁波雜訊的材料。而且，電動汽車、混合動力（hybrid）車等也朝向電氣化發展，需要可抑制在高溫下長時間操作的部件周圍的雜訊之材料。As the distance between electronic components is shortened due to their high-density assembly in the housing, they become susceptible to the influence of electromagnetic wave noise (noise) generated from electronic circuits, and it is easy to have a structure in which the heat energy generated from the electronic components is difficult to dissipate. Therefore, there is a need for electronic components that can operate at higher temperatures and materials that can suppress electromagnetic wave noise. In addition, electric vehicles, hybrid vehicles, etc. are also moving toward electrification, and materials that can suppress noise around components that operate at high temperatures for long periods of time are required.
已知可使用銀粉作為電磁波屏蔽（shield）材料（例如，請參照專利文獻1）。 然而，在使用銀粉的情況下，存在電磁波的屏蔽性不充分的問題。 [現有技術文獻] [專利文獻]It is known that silver powder can be used as an electromagnetic wave shield material (for example, refer to Patent Document 1). However, when silver powder is used, there is a problem of insufficient electromagnetic wave shielding properties. [Prior art documents] [Patent Document]
[專利文獻1]日本專利特開第2016-076444號公報[Patent Document 1] Japanese Patent Laid-Open No. 2016-076444
[發明所欲解決的課題][Problem to be solved by the invention]
本發明的目的係提供電磁波的屏蔽性優異之複合粒子、粉末，也提供電磁波的屏蔽性優異之成形體，而且還提供可適用於製造前述成形體的樹脂組合物。 [用於解決課題的手段]An object of the present invention is to provide composite particles and powders that are excellent in shielding properties against electromagnetic waves, to provide a molded article that is excellent in shielding properties against electromagnetic waves, and to provide a resin composition that can be suitably used for producing the molded objects. [Means used to solve problems]
可藉由下列的發明達成上述目的。The above object can be achieved by the following invention.
[1]一種複合粒子，其具備：由Mn鐵氧體所構成之母粒子、和包含選自由Au、Ag、Pt、Ni及Pd所組成的群組中至少1種的材料所構成之披覆層。[1] A composite particle including: a mother particle composed of Mn ferrite, and a coating composed of at least one material selected from the group consisting of Au, Ag, Pt, Ni, and Pd. layer.
[2]如[1]所述之複合粒子，其中前述Mn鐵氧體具有Mn的含量為3.5質量％以上20.0質量％以下、Fe的含量為50.0質量％以上70.0質量％以下的組成。[2] The composite particles according to [1], wherein the Mn ferrite has a composition in which the Mn content is 3.5 mass % or more and 20.0 mass % or less, and the Fe content is 50.0 mass % or more and 70.0 mass % or less.
[3]如[1]或[2]所述之複合粒子，其中前述Mn鐵氧體的居禮點為200℃以上500℃以下。[3] The composite particles according to [1] or [2], wherein the Curie point of the Mn ferrite is 200°C or more and 500°C or less.
[4]如[1]〜[3]中任一項所述之複合粒子，其中前述披覆層的厚度為10nm以上500nm以下。 [5]如[1]〜[4]中任一項所述之複合粒子，其中前述母粒子的形狀為真球狀。[4] The composite particle according to any one of [1] to [3], wherein the thickness of the coating layer is 10 nm or more and 500 nm or less. [5] The composite particle according to any one of [1] to [4], wherein the shape of the mother particle is a true spherical shape.
[6]一種粉末，其包含複數個[1]～[5]中任一項所述之複合粒子。 [7]如[6]所述之粉末，其中前述複合粒子的體積平均粒徑為1.0μm以上20μm以下。[6] A powder containing a plurality of composite particles according to any one of [1] to [5]. [7] The powder according to [6], wherein the volume average particle diameter of the composite particles is 1.0 μm or more and 20 μm or less.
[8]一種樹脂組合物，其包含[6]或[7]所述之粉末、和樹脂材料。 [9]一種成形體，其使用包含[6]或[7]所述之粉末、和樹脂材料之材料所製造而成。 [本發明的效果][8] A resin composition containing the powder described in [6] or [7] and a resin material. [9] A molded article produced using a material containing the powder described in [6] or [7] and a resin material. [Effects of the present invention]
根據本發明，能夠提供電磁波的屏蔽性優異之複合粒子、粉末，也提供電磁波的屏蔽性優異之成形體，而且還提供可適用於製造前述成形體的樹脂組合物。According to the present invention, it is possible to provide composite particles and powders excellent in electromagnetic wave shielding properties, a molded article excellent in electromagnetic wave shielding properties, and a resin composition suitable for producing the molded articles.
以下，針對本發明優選的實施形態進行詳細說明。 《複合粒子及粉末》 首先，針對本發明的複合粒子及粉末進行說明。Hereinafter, preferred embodiments of the present invention will be described in detail. "Composite Particles and Powders" First, the composite particles and powder of the present invention will be described.
本發明的複合粒子，具備由Mn鐵氧體（ferrite）所構成之母粒子、和包含選自由Au、Ag、Pt、Ni及Pd所組成的群組中至少1種的材料所構成之披覆層。The composite particles of the present invention include mother particles composed of Mn ferrite, and a coating composed of at least one material selected from the group consisting of Au, Ag, Pt, Ni, and Pd. layer.
而且，本發明的粉末包含複數個本發明的複合粒子。 藉此，能夠提供電磁波的屏蔽性優異之複合粒子、粉末。藉由具備電磁波的吸收性優異之母粒子、和電磁波的反射性優異的披覆層，以及上述兩者相乘作用之下，能夠得到這種優異的效果。Furthermore, the powder of the present invention contains a plurality of composite particles of the present invention. This makes it possible to provide composite particles and powders with excellent electromagnetic wave shielding properties. This excellent effect can be obtained by having mother particles that are excellent in absorbing electromagnetic waves, and a coating layer that is excellent in reflecting electromagnetic waves, and by the synergistic effect of the above two.
再者，藉由具備由Mn鐵氧體所構成之母粒子，相較於僅使用由以上所記載的金屬材料所構成之粒子的情況，能夠減輕重量。因此，可以適用於例如行動電話、智慧型手機、平板電腦等行動裝置。Furthermore, by providing mother particles composed of Mn ferrite, the weight can be reduced compared to the case of using only particles composed of the metal materials described above. Therefore, it can be applied to mobile devices such as mobile phones, smart phones, and tablet computers.
再者，能夠抑制昂貴金屬的使用量，整體上可以降低成本。Furthermore, the use of expensive metals can be suppressed and overall costs can be reduced.
再者，母粒子特別由各種鐵氧體之中的Mn鐵氧體所構成，因此不僅容易具有低電阻，還能夠得到以下效果，由於Mn的離子半徑與Fe的離子半徑相近，因此容易有規則性地進入晶體結構中，即使暴露於在形成披覆層時所使用的電鍍液、酸或鹼溶液，經過相對較長的時間也幾乎不會溶出Mn。再者，由於母粒子由Mn鐵氧體所構成，因此能夠使得母粒子與後續描述的披覆層之間的密合性變得優異，能夠長時間地穩定得到藉由本說明書中記載的本發明之效果。Furthermore, the mother particle is particularly composed of Mn ferrite among various ferrites, so it not only easily has low resistance, but also can obtain the following effects. Since the ionic radius of Mn is close to the ionic radius of Fe, it is easy to have regularity. Mn permanently enters the crystal structure, and even if it is exposed to the plating solution, acid or alkali solution used when forming the coating layer, Mn will hardly be eluted over a relatively long period of time. Furthermore, since the mother particles are composed of Mn ferrite, the adhesion between the mother particles and the coating layer described later can be excellent, and the invention described in this specification can be obtained stably for a long time. The effect.
再者，可以將複合粒子或粉末調整為除了黑色以外的顏色。更具體而言，藉由具備由包含Au的材料所構成之披覆層，可以將複合粒子、粉末的顏色調整為金色。再者，藉由具備包含選自由Ag、Pt、Ni及Pd所組成的群組中至少1種的材料所構成之披覆層，能夠將複合粒子、粉末的顏色適當地調整為白色至銀色之間的顏色。由此，例如，不僅可以將包含複合粒子、粉末的成形體的顏色適當地調整為白色至銀色之間的顏色，還可以使成形體包含著色劑（包括設置印刷層），進而將成形體調整為所需的顏色。Furthermore, the composite particles or powder can be adjusted to colors other than black. More specifically, by providing a coating layer made of a material containing Au, the color of the composite particles and powder can be adjusted to gold. Furthermore, by providing a coating layer composed of at least one material selected from the group consisting of Ag, Pt, Ni, and Pd, the color of the composite particles and powder can be appropriately adjusted to white to silver. color between. Thus, for example, not only can the color of a molded article containing composite particles or powder be appropriately adjusted to a color between white and silver, but the molded article can also be adjusted to include a colorant (including providing a printing layer). for the desired color.
再者，可以製備出導電性優異之包含複合粒子和粉末的成形體。特別是當與樹脂混合並成形時，控制外部磁場的同時施加電壓，使得粒子沿著磁力線配向排列，選擇性地在特定的方向上形成導電的路徑（通路），因此樹脂成形體的電阻能夠具有異向性。Furthermore, a molded body containing composite particles and powder having excellent electrical conductivity can be produced. Especially when mixed with resin and molded, a voltage is applied while controlling the external magnetic field so that the particles are aligned along the magnetic lines of force and selectively form conductive paths (paths) in specific directions. Therefore, the resistance of the resin molded body can be Anisotropy.
再者，例如，在使用本發明的粉末所製造的成形體中，粒子（複合粒子）可以在相對溫和的條件下適當地彼此接合。藉此，能夠更佳地兼顧成形體的電磁波之屏蔽性及機械強度。Furthermore, for example, in a shaped body produced using the powder of the present invention, particles (composite particles) can be appropriately bonded to each other under relatively mild conditions. This makes it possible to achieve a better balance between the electromagnetic wave shielding properties and the mechanical strength of the molded body.
再者，藉由控制由包含高導電性的貴金屬的材料所構成之披覆層的厚度，能夠控制複合粒子的磁導率的頻率特性。Furthermore, by controlling the thickness of the coating layer composed of a material containing a highly conductive noble metal, the frequency characteristics of the magnetic permeability of the composite particles can be controlled.
相對於此，沒有上述組成結構的粒子，無法得到上述優異的效果。On the other hand, particles without the above-mentioned composition structure cannot obtain the above-mentioned excellent effects.
例如，在不具有如以上所述的披覆層之粒子（單純為鐵氧體粒子）的情況下，無法充分地得到如以上所述的電磁波的反射效果，整體而言電磁波的屏蔽性不夠優異。再者，在使用包含粉末的組合物製造作為燒結體的成形體的情況下，為了充分地提高粒子的接合強度，通常需要設定比鐵氧體的居禮溫度更高的溫度，使得最終得到的成形體難以充分地發揮特性。再者，在比居禮溫度更低的溫度下進行燒結處理的情況下，成形體的強度變得不足。再者，由於粒子的顏色為亮度低的黑色，因此變得難以調整包含粉末的成形體的顏色。而且，包含粒子或粉末的成形體無法具有足夠優異的導電性。For example, in the case of particles that do not have a coating layer as described above (simply ferrite particles), the electromagnetic wave reflection effect as described above cannot be sufficiently obtained, and the overall electromagnetic wave shielding properties are not excellent enough. . Furthermore, when a composition containing powder is used to produce a molded body as a sintered body, in order to sufficiently improve the bonding strength of the particles, it is usually necessary to set a temperature higher than the Curie temperature of the ferrite so that the final obtained It is difficult for the molded article to fully exhibit its characteristics. Furthermore, when sintering is performed at a temperature lower than the Curie temperature, the strength of the molded body becomes insufficient. Furthermore, since the color of the particles is black with low brightness, it becomes difficult to adjust the color of the molded article containing the powder. Furthermore, a molded body containing particles or powder cannot have sufficiently excellent conductivity.
再者，即使在Mn鐵氧體粒子的表面上設置披覆層的情況下，當此披覆層的構成材料並非如以上所述時，也不能充分地得到如以上所述之電磁波的反射效果，無法使得電磁波整體的屏蔽性足夠優異。Furthermore, even when a coating layer is provided on the surface of the Mn ferrite particles, if the constituent material of the coating layer is not as described above, the electromagnetic wave reflection effect as described above cannot be sufficiently obtained. , it is impossible to make the overall electromagnetic wave shielding performance excellent enough.
再者，在單純使用金屬粒子（不具有由Mn鐵氧體所構成的母粒子之粒子）的情況下，不能充分地得到如以上所述之吸收電磁波的效果，無法使得電磁波整體的屏蔽性足夠優異。再者，粒子整體的比重增加，變得難以減輕粉末和成形體的重量。而且，一般而言，粉末和成形體的製造成本會增加。Furthermore, when simply using metal particles (particles without parent particles composed of Mn ferrite), the above-mentioned electromagnetic wave absorption effect cannot be fully obtained, and the overall electromagnetic wave shielding properties cannot be achieved. Excellent. Furthermore, the specific gravity of the entire particle increases, making it difficult to reduce the weight of the powder and the molded body. Moreover, in general, the manufacturing costs of powders and shaped bodies increase.
再者，當由其他的鐵氧體代替Mn鐵氧體構成母粒子時，相較於Mn鐵氧體粒子，體積電阻容易變高，且即使設置披覆層，電阻也難以降低，或者由於渦電流損耗所引起的低頻電磁波屏蔽效果也會降低。Furthermore, when the mother particles are composed of other ferrites instead of Mn ferrite, the volume resistance is likely to be higher than that of the Mn ferrite particles, and even if a coating layer is provided, the resistance is difficult to decrease, or due to vortex The low-frequency electromagnetic wave shielding effect caused by current loss will also be reduced.
（母粒子） 母粒子由Mn鐵氧體所構成。 而且，Mn鐵氧體一般是軟鐵氧體。 因此，藉由調整披覆層的厚度等，可以在寬頻範圍（例如，1MHz～1GHz）中容易地控制磁導率。(Mother particle) The mother particles are composed of Mn ferrite. Moreover, Mn ferrite is generally a soft ferrite. Therefore, by adjusting the thickness of the coating layer, etc., the magnetic permeability can be easily controlled in a wide frequency range (for example, 1 MHz to 1 GHz).
特別是，構成母粒子的Mn鐵氧體以具有Mn的含量為3.5質量％以上20.0質量％以下、Fe的含量為50.0質量％以上70.0質量％以下的組成為佳。In particular, the Mn ferrite constituting the mother particles preferably has a composition in which the Mn content is 3.5 mass % or more and 20.0 mass % or less, and the Fe content is 50.0 mass % or more and 70.0 mass % or less.
藉此，體積電阻變低，而且即使在低頻區域也可以容易得到由於渦電流損耗所引起的電磁波屏蔽效果。Thereby, the volume resistance becomes low, and the electromagnetic wave shielding effect caused by the eddy current loss can be easily obtained even in the low frequency region.
相對於此，在Mn的含量小於3.5質量％的情況下，雖然取決於製造條件，但不僅會變得容易氧化和變得容易減少磁化，體積電阻也會變高，由於渦電流損耗所引起的低頻電磁波屏蔽效果有可能會變小。On the other hand, when the Mn content is less than 3.5% by mass, not only does it become easier to oxidize and reduce magnetization, although it depends on the manufacturing conditions, but the volume resistance also becomes high, resulting in eddy current loss. The shielding effect of low-frequency electromagnetic waves may become smaller.
再者，在Mn的含量大於20.0質量％的情況下，Fe的含量相對降低，體積電阻容易變高，由於渦電流損耗所引起的低頻電磁波屏蔽效果有可能會變小。Furthermore, when the Mn content is greater than 20.0% by mass, the Fe content is relatively reduced, the volume resistance is likely to be high, and the low-frequency electromagnetic wave shielding effect caused by eddy current loss may be reduced.
再者，在Fe的含量小於50.0質量％的情況下，體積電阻容易變高，由於渦電流損耗所引起的低頻電磁波屏蔽效果有可能會變小。Furthermore, when the Fe content is less than 50.0% by mass, the volume resistance is likely to be high, and the low-frequency electromagnetic wave shielding effect due to eddy current loss may be reduced.
再者，在Fe的含量大於70.0質量％的情況下，雖然取決於製造條件，但不僅會變得容易氧化和變得容易減少磁化，體積電阻也會變高，由於渦電流損耗所引起的低頻電磁波屏蔽效果有可能會變小。Furthermore, when the content of Fe exceeds 70.0% by mass, although it depends on the manufacturing conditions, it not only becomes easy to oxidize and reduce magnetization, but also the volume resistance becomes high, and low frequency caused by eddy current loss The electromagnetic wave shielding effect may be reduced.
在前述Mn鐵氧體中，Mn的含量以3.5質量％以上20.0質量％以下為佳，以5.0質量％以上19.0質量％以下為較佳，且以6.4質量％以上18.0質量％以下為更佳。 如此一來，可以更顯著地發揮前述效果。In the Mn ferrite, the Mn content is preferably 3.5 mass% or more and 20.0 mass% or less, more preferably 5.0 mass% or more and 19.0 mass% or less, and more preferably 6.4 mass% or more and 18.0 mass% or less. In this way, the aforementioned effects can be exerted more significantly.
再者，在前述Mn鐵氧體中，Fe的含量以50.0質量％以上70.0質量％以下為佳，以51.0質量％以上66.0質量％以下為較佳，且以52.0質量％以上65.0質量％以下為更佳。 如此一來，可以更顯著地發揮前述效果。Furthermore, in the aforementioned Mn ferrite, the Fe content is preferably 50.0 mass% or more and 70.0 mass% or less, more preferably 51.0 mass% or more and 66.0 mass% or less, and 52.0 mass% or more and 65.0 mass% or less. Better. In this way, the aforementioned effects can be exerted more significantly.
構成母粒子的金屬元素（Fe、Mn等）的含量如以下所述進行測量。The content of metal elements (Fe, Mn, etc.) constituting the mother particles is measured as follows.
亦即，秤量0.2g的母粒子，在60ml的純水中加入20ml的1N的鹽酸以及20ml的1N的硝酸並進行加熱，製備出鐵氧體粒子完全溶解的水溶液，藉由使用ICP分析裝置（由島津製作所製造的ICPS-1000IV）進行測量，可以求得金屬元素的含量。That is, 0.2 g of mother particles are weighed, 20 ml of 1N hydrochloric acid and 20 ml of 1N nitric acid are added to 60 ml of pure water and heated to prepare an aqueous solution in which the ferrite particles are completely dissolved. By using an ICP analysis device ( By measuring with ICPS-1000IV (manufactured by Shimadzu Corporation), the content of metal elements can be determined.
Mn鐵氧體，以僅包含Fe和Mn作為金屬成分為佳。從上述觀點來看，Mn鐵氧體中所包含的除了Fe、Mn和O以外的所有成分（元素）的含量，以不超過雜質的含量為佳。 具體而言，Mn鐵氧體中所包含的除了Fe、Mn和O以外的所有成分（元素）的含量，以未滿0.1質量％為佳，以未滿0.05質量％為較佳，且以未滿0.01質量％為更佳。Mn ferrite preferably contains only Fe and Mn as metal components. From the above point of view, it is preferable that the content of all components (elements) other than Fe, Mn and O contained in Mn ferrite does not exceed the content of impurities. Specifically, the content of all components (elements) other than Fe, Mn and O contained in the Mn ferrite is preferably less than 0.1% by mass, more preferably less than 0.05% by mass, and less than 0.05% by mass. More than 0.01% by mass is better.
構成母粒子的Mn鐵氧體的居禮點（也稱為居禮溫度），以200℃以上500℃以下為佳，且以250℃以上480℃以下為較佳。The Curie point (also called Curie temperature) of the Mn ferrite constituting the mother particles is preferably 200°C or more and not more than 500°C, and more preferably 250°C or more and 480°C or less.
藉此，可以得到具有優異耐熱性之複合粒子和使用複合粒子所製造出的成形體等，例如，也可以適當地應用於在高溫環境下使用的成形體。Thereby, composite particles having excellent heat resistance and molded articles produced using the composite particles can be obtained. For example, the method can be suitably applied to molded articles used in high-temperature environments.
相對於此，當居禮溫度過低時，複合粒子和使用複合粒子所製造出的成形體等的耐熱性下降，可能導致可應用的部件、構件、環境等受到限制。On the other hand, when the Curie temperature is too low, the heat resistance of the composite particles and molded articles produced using the composite particles decreases, which may limit the applicable parts, components, environments, etc.
再者，雖然居禮溫度過高本身並不會造成問題，然而鐵氧體的居禮溫度由其組成決定，前述鐵氧體組合物的居禮溫度通常不超過500℃。Furthermore, although excessive Curie temperature itself does not cause problems, the Curie temperature of ferrite is determined by its composition. The Curie temperature of the aforementioned ferrite composition usually does not exceed 500°C.
上述的居禮點係藉由使用振動樣品型磁力計（VSM）（由東英工業所製造的VSM-5型），根據溫度變化測量鐵氧體粉末的磁化之變化所求得的。在所得到的磁化的溫度變化曲線中，可將從磁化正變成0之前一刻的低溫側之曲線的切線與磁化變成0的線交叉時的溫度設定為居禮點。The above-mentioned Curie point is obtained by measuring changes in magnetization of ferrite powder based on temperature changes using a vibrating sample magnetometer (VSM) (VSM-5 model manufactured by Dongying Industries). In the obtained temperature change curve of the magnetization, the temperature at which the tangent line of the curve on the low-temperature side just before the magnetization becomes 0 intersects with the line where the magnetization becomes 0 can be set as the Curie point.
再者，關於鐵氧體，可以使用振動樣品型磁性測量裝置，以測量飽和磁化強度、剩餘磁化強度、保磁力等的磁性特性。Furthermore, regarding ferrite, a vibrating sample type magnetic measurement device can be used to measure magnetic properties such as saturation magnetization, residual magnetization, coercive force, etc.
可以如下列所述求得上述磁性特性。亦即，首先，將內徑為5mm、高度為2mm的電池填充待測量的鐵氧體粉末，並放置於振動樣品型磁性測量裝置（由東英工業公司所製造的VSM-C7-10A）之中。接著，施加磁場並掃描至5kOe，然後減少施加的磁場，以產生遲滯曲線（Hysteresis curve）。之後，由此曲線的數據求得鐵氧體粉末的飽和磁化強度、剩餘磁化強度和保磁力。另外，關於作為後續描述的複合粒子的聚集體之粉末，也以相同的方式求得磁性特性。The above magnetic characteristics can be obtained as follows. That is, first, a battery with an inner diameter of 5 mm and a height of 2 mm is filled with ferrite powder to be measured and placed on a vibrating sample type magnetic measurement device (VSM-C7-10A manufactured by Dongying Industrial Co., Ltd.) middle. Next, a magnetic field is applied and swept to 5kOe, and then the applied magnetic field is reduced to produce a hysteresis curve. Then, the saturation magnetization, residual magnetization and coercive force of the ferrite powder are obtained from the data of this curve. In addition, the magnetic properties were also obtained in the same manner for the powder that is an aggregate of composite particles described later.
母粒子的飽和磁化強度的優選範圍為70～95emu/g，剩餘磁化強度的優選範圍為0.5～10emu/g，且保磁力的優選範圍為10～80Oe。 作為複合粒子的聚集體之粉末（複合粒子）的飽和磁化強度的優選範圍為30～90emu/g，剩餘磁化強度的優選範圍為0.5～9emu/g，且保磁力的優選範圍為10～80Oe。The preferred range of the saturation magnetization of the mother particles is 70 to 95 emu/g, the preferred range of the residual magnetization is 0.5 to 10 emu/g, and the preferred range of the coercive force is 10 to 80 Oe. The preferred range of the saturation magnetization of the powder (composite particles) which is an aggregate of composite particles is 30 to 90 emu/g, the preferred range of the residual magnetization is 0.5 to 9 emu/g, and the preferred range of the coercive force is 10 to 80 Oe.
母粒子的形狀並沒有特別限定，以真球狀為佳。 藉此，在使用根據本發明的粉末所製造出的成形體中，能夠進一步提高粉末的填充率，且能夠進一步提升電磁波的屏蔽性（吸收性、反射性）。The shape of the mother particles is not particularly limited, but a true spherical shape is preferred. Thereby, in the molded article produced using the powder according to the present invention, the filling rate of the powder can be further increased, and the electromagnetic wave shielding properties (absorptivity, reflectivity) can be further improved.
另外，在本說明書中，所謂真球狀，意味著真球狀或非常接近真球狀的形狀，具體而言，意味著形狀係數SF-1為100以上120以下。In addition, in this specification, the term "true spherical" means a true spherical shape or a shape very close to a true spherical shape. Specifically, it means that the shape coefficient SF-1 is 100 or more and 120 or less.
再者，母粒子的形狀係數SF-1以100以上120以下為佳，且以100以上115以下為較佳。Furthermore, the shape coefficient SF-1 of the mother particles is preferably from 100 to 120, and more preferably from 100 to 115.
可以如下列所述求得粒子的形狀係數SF-1。 首先，使用掃描電子顯微鏡（FE-SEM（SU-8020，由日立先端科技（High-Technologies）公司所製造））及能量色散型X射線分析裝置（EDX）（由堀場製作所所製造的E-MAX），將放大倍率設定成大約3～50個粒子落入1個視野之中（例如，在後續描述的實施例及比較例中，放大倍率設定為1000～2000倍），並使用EDX附帶的功能之粒子分析功能，自動測量1000個以上的粒子之等效圓直徑、圓周、長度、寬度、面積。The shape coefficient SF-1 of the particles can be obtained as follows. First, a scanning electron microscope (FE-SEM (SU-8020, manufactured by Hitachi High-Technologies)) and an energy-dispersive X-ray analyzer (EDX) (E-MAX manufactured by Horiba Manufacturing Co., Ltd. were used ), set the magnification so that approximately 3 to 50 particles fall into one field of view (for example, in the embodiments and comparative examples described later, the magnification is set to 1000 to 2000 times), and use the functions included with EDX The particle analysis function can automatically measure the equivalent circle diameter, circumference, length, width, and area of more than 1,000 particles.
在所得到的數據中，明顯彼此重疊的粒子（圓周長度為從等效圓直徑所計算出的圓周長度的1.8倍以上的粒子），除了細粉末（等效圓直徑比1μm更小的粉末）以外，將粒子的最大長度（水平費雷特（Feret）徑）設為R，面積設為投影面積S，以下列式計算出SF-1的值。粒子形狀越接近球形，則此值越接近100。In the obtained data, particles that clearly overlap each other (particles whose circumferential length is more than 1.8 times the circumferential length calculated from the equivalent circle diameter), except for fine powders (powders with an equivalent circle diameter smaller than 1 μm) In addition, assuming that the maximum length of the particle (horizontal Feret diameter) is R and the area is the projected area S, the value of SF-1 is calculated according to the following formula. The closer the particle shape is to a sphere, the closer this value is to 100.
SF-1=（R2 /S）×（π/4）×100（式中的R表示粒子的最大長度（水平費雷特徑）（μｍ），且S表示面積（投影面積，單位為μm2 ））。SF-1=(R 2 /S) × (π/4) × 100 (R in the formula represents the maximum length of the particle (horizontal Feret diameter) (μm), and S represents the area (projected area, unit is μm) 2 )).
SF-1可以每1粒子計算200個粒子以上，並採用平均值作為粉末的SF-1。SF-1 can count more than 200 particles per particle, and the average value is used as the SF-1 of the powder.
構成單一的複合粒子之母粒子，例如，可以是由單一的粒子所構成，或者也可以是由複數微粒子的接合物（包含凝集體）。The mother particle constituting a single composite particle may, for example, be composed of a single particle, or may be a joint (including an aggregate) of a plurality of fine particles.
（披覆層） 披覆層係覆蓋母粒子的至少一部分的膜層。而且，披覆層由包含選自由Au、Ag、Pt、Ni及Pd所組成的群組中至少1種的材料所構成。(Coating layer) The coating layer is a film layer that covers at least part of the mother particles. Furthermore, the coating layer is composed of at least one material selected from the group consisting of Au, Ag, Pt, Ni, and Pd.
上述金屬元素（Au、Ag、Pt、Ni、Pd）可以作為單一金屬或者也可以作為合金的構成成分而包含於披覆層中。The above-mentioned metal elements (Au, Ag, Pt, Ni, Pd) may be included in the coating layer as a single metal or as a constituent component of an alloy.
披覆層可以由包含選自由Au、Ag、Pt、Ni及Pd所組成的群組中至少1種的材料所構成，而其中，作為披覆層的構成材料，以Au及Ag之中的至少一者為佳。The coating layer may be composed of at least one material selected from the group consisting of Au, Ag, Pt, Ni, and Pd, and the constituent material of the coating layer may be at least one of Au and Ag. One is better.
在構成前述群組的金屬之中，Au、Ag具有相對較低的熔點，在製造作為燒結體的成形體的情況下，即使在相對較低的溫度下進行燒結，複合粒子也能夠適當地彼此接合。再者，藉由控制披覆層的厚度，能夠更適當地控制複合粒子的磁導率的頻率特性。Among the metals constituting the aforementioned group, Au and Ag have relatively low melting points. When producing a compact as a sintered body, the composite particles can properly interact with each other even if they are sintered at a relatively low temperature. Engagement. Furthermore, by controlling the thickness of the coating layer, the frequency characteristics of the magnetic permeability of the composite particles can be more appropriately controlled.
披覆層中Au及Ag的含量之和，以80質量％以上為佳，且以90質量％以上為較佳。 如此一來，可以更顯著地發揮前述效果。The total content of Au and Ag in the coating layer is preferably 80 mass% or more, and more preferably 90 mass% or more. In this way, the aforementioned effects can be exerted more significantly.
雖然披覆層的厚度並沒有特別限定，但以10nm以上且500nm以下為佳，以10nm以上400nm以下為較佳，且以10nm以上300nm以下為更佳。Although the thickness of the coating layer is not particularly limited, it is preferably from 10 nm to 500 nm, more preferably from 10 nm to 400 nm, and more preferably from 10 nm to 300 nm.
如此一來，能夠在抑制金屬的使用量的同時更有效地反射電磁波。 可以藉由以下所述之方法求得披覆層的厚度。 亦即，將粒子嵌入樹脂之中，使用離子研磨（Ion milling）裝置進行粒子的剖面處理，並製作所得到的拍攝用樣本。 可以利用FE-SEM拍攝所得到的拍攝用樣本，並使用影像分析軟體或影像之中比例尺的長度（所記載的值）、以及根據在SEM影像中的比例尺的標尺之實際測量值和根據披覆層的厚度的標尺之實際測量值計算得到。使用了由日立先端科技所製造的SU-8020作為Fe-SEM。使用了由日立先端科技所製造的IM-4000作為離子研磨裝置。使用了環氧樹脂作為嵌入用樹脂。In this way, electromagnetic waves can be reflected more effectively while reducing the amount of metal used. The thickness of the coating layer can be determined by the method described below. That is, the particles are embedded in the resin, the particles are cross-sectionally processed using an ion milling device, and the resulting imaging sample is produced. You can use the sample for photography obtained by FE-SEM, and use image analysis software or the length (recorded value) of the scale bar in the image, and the actual measured value of the ruler based on the scale bar in the SEM image and the coating. The thickness of the layer is calculated from the actual measured value of the scale. SU-8020 manufactured by Hitachi Advanced Technologies was used as Fe-SEM. IM-4000 manufactured by Hitachi Advanced Technologies was used as the ion grinding device. Epoxy resin was used as the embedding resin.
假設複合粒子的粒徑為D[μm]、披覆層的厚度為T[μm]，則以滿足0.0010≤T/D≤0.10的關係式為佳，且以滿足0.0030≤T/D≤0.080的關係式為較佳，且以滿足0.0050≤T/D≤0.050的關係式為更佳。 另外，上述複合粒子的粒徑為體積平均粒徑。可以藉由後續描述的方法測量體積平均粒徑。Assuming that the particle diameter of the composite particles is D [μm] and the thickness of the coating layer is T [μm], it is better to satisfy the relational expression of 0.0010≤T/D≤0.10, and to satisfy the relation of 0.0030≤T/D≤0.080 The relational expression is preferred, and the relational expression satisfying 0.0050≤T/D≤0.050 is even more preferred. In addition, the particle diameter of the above-mentioned composite particles is the volume average particle diameter. The volume average particle size can be measured by the method described later.
如此一來，能夠使得電磁波的吸收與電磁波的反射兩者之間的平衡更佳，且整體上的電磁波屏蔽效果特別優異。In this way, the balance between the absorption of electromagnetic waves and the reflection of electromagnetic waves can be better achieved, and the overall electromagnetic wave shielding effect is particularly excellent.
本發明的複合粒子，可以如前述具有母粒子和披覆層，且也可以具有其他的組成成分。The composite particles of the present invention may have mother particles and a coating layer as mentioned above, and may also have other components.
例如，複合粒子也可以在母粒子與披覆層之間具有至少1層的中間層。For example, the composite particles may have at least one intermediate layer between the mother particles and the coating layer.
再者，在前述披覆層的表面上，也可以設置由除了Au、Ag、Pt、Ni及Pd以外的材料所構成的塗佈層。作為這種塗佈層，例如，可列舉出使用矽烷偶合劑等的各種偶合劑之表面處理層。Furthermore, a coating layer made of materials other than Au, Ag, Pt, Ni, and Pd may be provided on the surface of the coating layer. Examples of such a coating layer include surface treatment layers using various coupling agents such as silane coupling agents.
再者，在母粒子的表面上，除了由包含選自由Au、Ag、Pt、Ni及Pd所組成的群組中至少1種的材料所構成之披覆層（第1披覆層）以外，也可以設置由Au、Ag、Pt、Ni及Pd以外的材料所構成之其他披覆層（第2披覆層）。Furthermore, on the surface of the mother particle, in addition to a coating layer (first coating layer) composed of at least one material selected from the group consisting of Au, Ag, Pt, Ni, and Pd, Another coating layer (second coating layer) made of materials other than Au, Ag, Pt, Ni, and Pd may be provided.
複合粒子的體積平均粒徑以1.0μm以上20μm以下為佳，以1.5μm以上18μm以下為較佳，且以2.0μm以上15μm以下為更佳。The volume average particle diameter of the composite particles is preferably from 1.0 μm to 20 μm, more preferably from 1.5 μm to 18 μm, and more preferably from 2.0 μm to 15 μm.
如此一來，在將複合粒子和樹脂混合以製作成形體時，粒子之間的空隙變小，且容易產生磁性材料（母粒子）被緻密地填充的狀態。In this way, when the composite particles and the resin are mixed to produce a molded body, the gaps between the particles become smaller and the magnetic material (mother particles) is likely to be densely filled.
藉由以下所述之測量方法求得體積平均粒徑。亦即，首先，將10g作為試驗材料的粉末和80ml的水放置於100ml的燒杯中，並加入2滴分散劑（六偏磷酸鈉（Sodium hexametaphosphate））。接著，使用超音波均化器（homogenizer，由SMT股份有限公司所製造的UH-150型）進行分散。此時，將超音波均化器的輸出程度設定為4，並進行20秒的分散。之後，去除燒杯表面上形成的泡沫，並將其放置於雷射衍射型粒度分佈測量裝置（由島津製作所製造的SALD-7500nano）中進行測量。此時的測量條件為泵速為7，折射率為1.70-0.50i，且內部超音波照射時間為30。The volume average particle size is determined by the measurement method described below. That is, first, 10 g of powder as a test material and 80 ml of water are placed in a 100 ml beaker, and 2 drops of dispersant (sodium hexametaphosphate) are added. Next, an ultrasonic homogenizer (UH-150 model manufactured by SMT Co., Ltd.) was used for dispersion. At this time, the output level of the ultrasonic homogenizer was set to 4, and dispersion was performed for 20 seconds. After that, the foam formed on the surface of the beaker was removed, and it was placed in a laser diffraction type particle size distribution measuring device (SALD-7500nano manufactured by Shimadzu Corporation) for measurement. The measurement conditions at this time are that the pump speed is 7, the refractive index is 1.70-0.50i, and the internal ultrasonic irradiation time is 30.
在由Mn鐵氧體所構成的母粒子上形成披覆層之複合粒子，容易在水中聚集，有時無法進行高精準度的測量。在這種情況下，可以使用上述粒子的影像分析數據計算體積平均粒徑。Composite particles in which a coating layer is formed on a mother particle made of Mn ferrite tend to aggregate in water, making it impossible to perform high-precision measurements in some cases. In this case, the volume average particle size can be calculated using the image analysis data of the above particles.
亦即，可以在粒子分析結果中利用計算SF-1時所使用的粒子數據，將第i個粒子的等效圓直徑設為di ，且粒子的體積設為Vi ，以Vi = 4/3×π×（di /2）3 算出Vi ，且以D50=Σ（Vi ‧di ）/Σ（Vi ）算出體積平均直徑。That is, the particle data used in calculating SF-1 can be used in the particle analysis results, and the equivalent circle diameter of the i-th particle is set to d i , and the volume of the particle is set to Vi , so that Vi = 4 /3×π×(d i /2) 3 Calculate V i , and calculate the volume average diameter using D50=Σ(V i ‧d i )/Σ(V i ).
本發明的粉末（複合粒子的聚集體）的BET比表面積，以1m2 /g以上9m2 /g以下為佳，以1m2 /g以上8m2 /g以下為較佳，且以3m2 /g以上8m2 /g以下為更佳。The BET specific surface area of the powder (aggregation of composite particles) of the present invention is preferably 1 m 2 /g or more and 9 m 2 /g or less, more preferably 1 m 2 /g or more and 8 m 2 /g or less, and 3 m 2 /g or more. More than g and less than 8m 2 /g is better.
如此一來，能夠更加提升電磁波的屏蔽性，且同時進一步提升本發明的成形體中的複合粒子與樹脂材料之間的密合性，使得成形體能夠具有特別優異的耐久性。In this way, the shielding property of electromagnetic waves can be further improved, and at the same time, the adhesion between the composite particles and the resin material in the molded article of the present invention can be further improved, so that the molded article can have particularly excellent durability.
另外，可藉由使用比表面積測量裝置（型號：Macsorb HM model-1208（由MOUNTECH公司所製造））測量得到BET比表面積。In addition, the BET specific surface area can be measured by using a specific surface area measuring device (model: Macsorb HM model-1208 (manufactured by MOUNTECH)).
本發明的粉末（複合粒子的聚集體）的振實（Tap）密度，以1.8g/cm3 以上3.0g/cm3 以下為佳，且以2.0g/cm3 以上3.0g/cm3 以下為較佳。 如此一來，變得容易提高本發明的成形體中複合粒子的填充率。The tap density of the powder (aggregation of composite particles) of the present invention is preferably 1.8 g/cm 3 or more and 3.0 g/cm 3 or less, and is preferably 2.0 g/cm 3 or more and 3.0 g/cm 3 or less. Better. This makes it easy to increase the filling rate of the composite particles in the molded article of the present invention.
另外，在本說明書中，振實密度係指根據JIS R1628的測量方法所求得的密度。 作為振實（Tapping）裝置，可以使用USP振實密度測量裝置（粉末測試儀（Powder tester）PT-X，由細川密克朗（Hosokawa Micron）公司所製造）。In addition, in this specification, the tap density means the density calculated|required based on the measurement method of JIS R1628. As the tapping device, a USP tap density measuring device (Powder tester PT-X, manufactured by Hosokawa Micron) can be used.
本發明的粉末在25℃下的電阻率（體積電阻率），以1.0×10-5 以上10Ω‧cm以下為佳，以1.0×10-5 以上1.0×10-1Ω ‧cm以下為較佳，且以1.0×10-5 以上1.0×10-2Ω ‧cm以下為更佳。The resistivity (volume resistivity) of the powder of the present invention at 25°C is preferably not less than 1.0×10 -5 and not more than 10Ω‧cm, and preferably not less than 1.0×10 -5 and not more than 1.0×10 -1Ω‧cm . And it is more preferably 1.0×10 -5 or more and 1.0×10 -2Ω‧cm or less.
本發明的母粒子在25℃下的電阻率（體積電阻率），以1.0×102 ~5.0×108 Ω‧cm為佳，以1×102 ~1.0×107 Ω‧cm為較佳，且以1.0×103 ～1.0×106 Ω‧cm為更佳。The resistivity (volume resistivity) of the mother particles of the present invention at 25°C is preferably 1.0×10 2 ~5.0×10 8 Ω‧cm, and preferably 1×10 2 ~1.0×10 7 Ω‧cm , and 1.0×10 3 to 1.0×10 6 Ω‧cm is more preferred.
如此一來，在將複合粒子和樹脂混合以製作成形體時（雖然也取決於與樹脂的混合比），變得容易形成導電路徑，能夠更有效地降低樹脂成形體的電阻。In this way, when the composite particles and resin are mixed to produce a molded article (although it also depends on the mixing ratio with the resin), it becomes easier to form a conductive path, and the resistance of the resin molded article can be reduced more effectively.
再者，本發明的粉末可以包含複數個本發明的複合粒子，而且也可以還包含除了本發明的複合粒子以外的粒子。Furthermore, the powder of the present invention may contain a plurality of composite particles of the present invention, and may further contain particles other than the composite particles of the present invention.
在這種情況下，在本發明的粉末中本發明的複合粒子以外的粒子的含量，以10質量％以下為佳，以5.0質量％以下為較佳，且以1.0質量％以下為更佳。 如此一來，可以更加確實地發揮前述本發明的效果。In this case, the content of particles other than the composite particles of the present invention in the powder of the present invention is preferably 10 mass% or less, more preferably 5.0 mass% or less, and more preferably 1.0 mass% or less. In this way, the above-mentioned effects of the present invention can be exerted more reliably.
《複合粒子的製造方法》 接著，針對根據本發明的複合粒子的製造方法進行說明。"Method for Manufacturing Composite Particles" Next, a method for producing composite particles according to the present invention will be described.
可以在以預定的方法所製造出的Mn鐵氧體粒子的表面上，藉由各種電鍍方法形成披覆層，以製造出本發明的複合粒子。The composite particles of the present invention can be produced by forming a coating layer on the surface of Mn ferrite particles produced by a predetermined method by various electroplating methods.
作為用於形成披覆層的電鍍方法，例如，可列舉出電解電鍍、無電鍍等的濕式電鍍法、和真空氣相沉積、濺射（sputtering）、離子電鍍（ion plating）等的乾式電鍍法等，其中以濕式電鍍法為佳，且以無電鍍法為較佳。Examples of the plating method for forming the coating layer include wet plating methods such as electrolytic plating and electroless plating, and dry plating methods such as vacuum vapor deposition, sputtering, and ion plating. Methods, etc., among which wet plating method is preferred, and electroless plating method is preferred.
作為母粒子的Mn鐵氧體粒子，可以藉由任何方法製造，例如可以藉由如以下所述之方法適當地製造。Mn ferrite particles as mother particles can be produced by any method. For example, they can be produced appropriately by the method described below.
例如，藉由將以預定的成分所調配出的鐵氧體原料，在大氣中熱噴塗然後急速冷卻凝固（第1方法），可以適當地製造出作為母粒子的Mn鐵氧體粒子。 在此方法中，可以適當地使用造粒物作為鐵氧體原料。For example, Mn ferrite particles as mother particles can be appropriately produced by thermally spraying a ferrite raw material prepared with a predetermined component in the atmosphere and then rapidly cooling and solidifying it (first method). In this method, granulated materials can be suitably used as the ferrite raw material.
鐵氧體原料的調配方法並沒有特別限定，例如，可以使用乾式方法，或者也可以使用濕式方法。再者，可以組合乾式和濕式使用。The preparation method of the ferrite raw material is not particularly limited. For example, a dry method or a wet method may be used. Furthermore, dry and wet use can be combined.
以下列舉出鐵氧體原料（造粒物）的調配方法的一範例。 亦即，以對應於待製造出的Mn鐵氧體粒子（母粒子）的成分，將包含金屬元素的複數種原料稱重並混合之後，加入水並粉碎而製成漿料。將所製成的粉碎漿料用噴霧乾燥器（Spray dryer）造粒並分級，以調配出具有預定的粒徑的造粒物。An example of the preparation method of the ferrite raw material (granulated material) is given below. That is, a plurality of raw materials including metal elements are weighed and mixed with components corresponding to the Mn ferrite particles (mother particles) to be produced, and then water is added and pulverized to form a slurry. The prepared pulverized slurry is granulated and classified using a spray dryer to prepare granulated materials having a predetermined particle size.
再者，以下列舉出氧體原料（造粒物）的調配方法的另一範例。 亦即，以對應於待製造出的Mn鐵氧體粒子（母粒子）的成分，將包含金屬元素的複數種原料稱重並混合之後，進行乾式粉碎，以粉碎分散各原料，並將此混合物用造粒機（Granulator）造粒並分級，以調配出具有預定的粒徑的造粒物。 將如以上所述調配的造粒物在大氣中進行熱噴塗進而鐵氧體化。In addition, another example of the preparation method of the oxygen body raw material (granulated material) is listed below. That is, after weighing and mixing a plurality of raw materials containing metal elements with components corresponding to the Mn ferrite particles (mother particles) to be produced, dry pulverization is performed to pulverize and disperse each raw material, and the mixture is A granulator (Granulator) is used to granulate and classify to prepare granulated materials having a predetermined particle size. The granulated material prepared as above is thermally sprayed in the air and ferriteized.
對於熱噴塗，可以使用燃燒氣體和氧氣之混合氣體作為可燃性氣體燃燒火焰。For thermal spraying, a mixture of combustion gas and oxygen can be used as a flammable gas combustion flame.
燃燒氣體與氧氣的體積比，以1：3.5以上1：6.0以下為佳。 如此一來，可以適當地促進由於揮發材料的冷凝而形成粒徑相對較小的粒子。再者，可以適當地調整所得到的Mn鐵氧體粒子（母粒子）的形狀。再者，可以省略或者簡化後續的製程中的分級等的處理步驟，因而能夠進一步提高Mn鐵氧體粒子（母粒子）的生產率。再者，可以減少在後續的製程中藉由分級而去除的粒子的比例，因而能夠進一步提高Mn鐵氧體粒子（母粒子）的產率。The volume ratio of combustion gas to oxygen is preferably 1:3.5 or more and 1:6.0 or less. In this way, the formation of relatively small particles due to condensation of volatile materials can be appropriately promoted. Furthermore, the shape of the obtained Mn ferrite particles (mother particles) can be appropriately adjusted. Furthermore, processing steps such as classification in subsequent processes can be omitted or simplified, so the productivity of Mn ferrite particles (mother particles) can be further improved. Furthermore, the proportion of particles removed by classification in the subsequent process can be reduced, thereby further improving the yield of Mn ferrite particles (mother particles).
例如，相對於燃燒氣體為10Nm3 hr，氧氣的使用比例為35Nm3 hr以上60Nm3 hr以下。For example, with respect to the combustion gas of 10Nm 3 hr, the usage ratio of oxygen is 35Nm 3 hr or more and 60Nm 3 hr or less.
作為用於熱噴塗的燃燒氣體，可列舉出丙烷氣體、丙烯氣體、乙炔氣體等。其中，可以適合使用丙烷氣體。Examples of the combustion gas used for thermal spraying include propane gas, propylene gas, acetylene gas, and the like. Among them, propane gas can be suitably used.
再者，為了將造粒物輸送至可燃性氣體之中，可以使用氮氣、氧氣、空氣等作為造粒物的輸送氣體。 輸送造粒物的流速，以20m/秒以上60m/秒以下為佳。Furthermore, in order to transport the granulated materials into the flammable gas, nitrogen, oxygen, air, etc. can be used as the transport gas for the granulated materials. The flow rate for transporting granulated materials is preferably between 20m/sec and 60m/sec.
再者，前述熱噴塗以在1000℃以上3500℃以下的溫度下進行為佳，且以在2000℃以上3500℃以下的溫度下進行為較佳。Furthermore, the thermal spraying is preferably carried out at a temperature of not less than 1000°C and not more than 3500°C, and more preferably at a temperature of not less than 2000°C and not more than 3500°C.
藉由滿足上述的條件，可以更加適當地促進由於揮發材料的冷凝而形成粒徑相對較小的粒子。再者，可以更加適當地調整所得到的Mn鐵氧體粒子（母粒子）的形狀。再者，可以省略或者簡化後續的製程中的分級等的處理步驟，因而能夠進一步提高Mn鐵氧體粒子（母粒子）的生產率。再者，可以減少在後續的製程中藉由分級而去除的粒子的比例，因而能夠進一步提高Mn鐵氧體粒子（母粒子）的產率。By satisfying the above conditions, the formation of particles with a relatively small particle size due to condensation of volatile materials can be more appropriately promoted. Furthermore, the shape of the obtained Mn ferrite particles (mother particles) can be adjusted more appropriately. Furthermore, processing steps such as classification in subsequent processes can be omitted or simplified, so the productivity of Mn ferrite particles (mother particles) can be further improved. Furthermore, the proportion of particles removed by classification in the subsequent process can be reduced, thereby further improving the yield of Mn ferrite particles (mother particles).
如此一來，熱噴塗且鐵氧體化的粒子，在水中或在大氣中急速冷卻凝固，並藉由旋風分離器（cyclone）及/或過濾器（filter）收集。As a result, the thermally sprayed and ferrite particles are rapidly cooled and solidified in water or in the atmosphere, and are collected by a cyclone and/or filter.
之後，藉由旋風分離器及/或收集用過濾器所回收的Mn鐵氧體粒子，根據需求進行分級。作為分級方法，可使用現有的風力分級、篩網（mesh）過濾法、沉降法等，調整所需的粒徑。另外，也可以使用旋風分離器等，將粒徑大的粒子分離並回收。After that, the Mn ferrite particles recovered by the cyclone separator and/or the collection filter are classified according to the needs. As a classification method, existing wind classification, mesh filtration method, sedimentation method, etc. can be used to adjust the required particle size. In addition, a cyclone separator or the like may be used to separate and recover particles with large particle diameters.
再者，可以藉由以下所述之方法（第2方法）適當地製造Mn鐵氧體粒子（母粒子）。In addition, Mn ferrite particles (mother particles) can be appropriately produced by the method (second method) described below.
亦即，例如可以藉由具有將包含鐵氧體原料的組合物造粒（pellet）且預煅燒以得到預煅燒體之預煅燒步驟、和將預煅燒體粉碎並分級之後對預煅燒粉進行煅燒之主要煅燒步驟的方法，製造Mn鐵氧體粒子（母粒子）。That is, for example, the precalcined powder can be calcined by having a precalcining step of pelletizing and preliminarily calcining the composition containing the ferrite raw material to obtain a precalcined body, and crushing and classifying the precalcined body. The main calcination step is a method to produce Mn ferrite particles (mother particles).
如此一來，能夠有效地製造出用於製造具有如以上所述之形狀、尺寸的複合粒子之Mn鐵氧體粒子。再者，在製造過程中，不同於使用酸或鹼的濕式造粒法，能夠有效地防止源自酸或鹼的雜質等殘留於Mn鐵氧體粒子（母粒子）之中，可以進一步提高複合粒子和使用複合粒子所製造的樹脂組合物、成形體的耐久性、可靠性。 可以藉由使用壓力成型機適當地進行粒子的製作。In this way, Mn ferrite particles for producing composite particles having the above-described shape and size can be efficiently produced. Furthermore, during the manufacturing process, unlike the wet granulation method that uses acid or alkali, impurities derived from acids or alkali can be effectively prevented from remaining in the Mn ferrite particles (mother particles), which can further improve Durability and reliability of composite particles and resin compositions and molded articles produced using composite particles. Particles can be produced appropriately by using a pressure molding machine.
預煅燒步驟中的加熱溫度並沒有特別限定，但以600℃以上1200℃以下為佳，以650℃以上1000℃以下為較佳，且以700℃以上900℃以下為更佳。The heating temperature in the preliminary calcination step is not particularly limited, but it is preferably 600°C or more and not more than 1,200°C, more preferably 650°C or more and not more than 1,000°C, and more preferably 700°C or more and not more than 900°C.
由此，可以適當地進行預煅燒體的粉碎，能夠更加適當地製造出用於製造具有如以上所述之形狀、尺寸的複合粒子之Mn鐵氧體粒子。 在預煅燒步驟中，也可以進行2階段以上的加熱處理（煅燒處理）。Thereby, the preliminary calcined body can be pulverized appropriately, and Mn ferrite particles for producing composite particles having the above-described shape and size can be more appropriately produced. In the preliminary calcination step, two or more stages of heat treatment (calcining treatment) may be performed.
在主要煅燒步驟中，提供經過粉碎處理且為不固定形狀的預煅燒體及/或經過粉碎處理（在較高溫度下煅燒）的燒結體。 主要煅燒步驟所提供的預煅燒體及/或燒結體的體積平均粒徑，以0.5μm以上30μm以下為佳，且以0.5μm以上且20μm以下為較佳。或者，在不固定形狀的預煅燒體及/或燒結體的粒徑小的情況下，以使用聚集了複數粒子之造粒物為佳。在使用造粒物的情況下，也可以調整造粒物的黏合劑（binder）的量，使得原料粒子容易分散於熱噴塗框架（frame）。In the main calcining step, a precalcined body that has been pulverized and has an irregular shape and/or a sintered body that has been pulverized (calcined at a higher temperature) is provided. The volume average particle size of the pre-calcined body and/or sintered body provided in the main calcination step is preferably 0.5 μm or more and 30 μm or less, and more preferably 0.5 μm or more and 20 μm or less. Alternatively, when the particle size of the pre-calcined body and/or the sintered body is not fixed, it is preferable to use a granulated product in which a plurality of particles are aggregated. When using granulated materials, the amount of binder in the granulated materials can also be adjusted so that the raw material particles can be easily dispersed in the thermal spray frame.
如此一來，能夠有效地製造出用於製造具有如以上所述之形狀、尺寸的複合粒子之Mn鐵氧體粒子。再者，可以省略或者簡化後續的製程中的分級等的處理步驟，因而能夠進一步提高Mn鐵氧體粒子（母粒子）的生產率。再者，可以減少在後續的製程中藉由分級而去除的粒子的比例，因而能夠進一步提高Mn鐵氧體粒子（母粒子）的產率。In this way, Mn ferrite particles for producing composite particles having the above-described shape and size can be efficiently produced. Furthermore, processing steps such as classification in subsequent processes can be omitted or simplified, so the productivity of Mn ferrite particles (mother particles) can be further improved. Furthermore, the proportion of particles removed by classification in the subsequent process can be reduced, thereby further improving the yield of Mn ferrite particles (mother particles).
例如，以對藉由將預煅燒體的粉末（藉由粉碎、分級處理所得到的粉末）造粒所得到的造粒物進行主要煅燒步驟為佳。For example, it is preferable to perform the main calcining step on a granulated product obtained by granulating the powder of the pre-calcined body (powder obtained by crushing and classifying treatment).
如此一來，能夠有效地製造出用於製造具有如以上所述之形狀、尺寸的複合粒子之Mn鐵氧體粒子。再者，可以省略或者簡化後續的製程中的分級等的處理步驟，因而能夠進一步提高Mn鐵氧體粒子的生產率。再者，可以減少在後續的製程中藉由分級而去除的粒子的比例，因而能夠進一步提高Mn鐵氧體粒子的產率。In this way, Mn ferrite particles for producing composite particles having the above-described shape and size can be efficiently produced. Furthermore, processing steps such as classification in subsequent processes can be omitted or simplified, so the productivity of Mn ferrite particles can be further improved. Furthermore, the proportion of particles removed by classification in subsequent processes can be reduced, thereby further improving the yield of Mn ferrite particles.
可以藉由在大氣中熱噴塗預煅燒體的粉末，以適當地進行主要煅燒。 對於熱噴塗，可以使用燃燒氣體和氧氣之混合氣體作為可燃性氣體燃燒火焰。The main calcination can be suitably carried out by thermal spraying the powder of the precalcined body in the atmosphere. For thermal spraying, a mixture of combustion gas and oxygen can be used as a flammable gas combustion flame.
燃燒氣體與氧氣的體積比，以1：3.5以上1：6.0以下為佳。 如此一來，可以適當地促進由於揮發材料的冷凝而形成粒徑相對較小的Mn鐵氧體粒子。再者，可以更加適當地調整所得到的Mn鐵氧體粒子的形狀。再者，可以省略或者簡化後續的製程中的分級等的處理步驟，因而能夠進一步提高Mn鐵氧體粒子的生產率。再者，可以減少在後續的製程中藉由分級而去除的粒子的比例，因而能夠進一步提高Mn鐵氧體粒子的產率。The volume ratio of combustion gas to oxygen is preferably 1:3.5 or more and 1:6.0 or less. In this way, the formation of Mn ferrite particles with relatively small particle sizes due to condensation of volatile materials can be appropriately promoted. Furthermore, the shape of the obtained Mn ferrite particles can be adjusted more appropriately. Furthermore, processing steps such as classification in subsequent processes can be omitted or simplified, so the productivity of Mn ferrite particles can be further improved. Furthermore, the proportion of particles removed by classification in subsequent processes can be reduced, thereby further improving the yield of Mn ferrite particles.
例如，相對於燃燒氣體為10Nm3 hr，氧氣的使用比例為35Nm3 hr以上60Nm3 hr以下。For example, with respect to the combustion gas of 10Nm 3 hr, the usage ratio of oxygen is 35Nm 3 hr or more and 60Nm 3 hr or less.
作為用於熱噴塗的燃燒氣體，可列舉出丙烷氣體、丙烯氣體、乙炔氣體等。其中，可以適合使用丙烷氣體。Examples of the combustion gas used for thermal spraying include propane gas, propylene gas, acetylene gas, and the like. Among them, propane gas can be suitably used.
再者，為了將造粒物輸送至可燃性氣體之中，可以使用氮氣、氧氣、空氣等作為造粒物的輸送氣體。 輸送造粒物的流速，以20m/秒以上60m/秒以下為佳。Furthermore, in order to transport the granulated materials into the flammable gas, nitrogen, oxygen, air, etc. can be used as the transport gas for the granulated materials. The flow rate for transporting granulated materials is preferably between 20m/sec and 60m/sec.
再者，前述熱噴塗以在1000℃以上3500℃以下的溫度下進行為佳，且以在2000℃以上3500℃以下的溫度下進行為較佳。Furthermore, the thermal spraying is preferably carried out at a temperature of not less than 1000°C and not more than 3500°C, and more preferably at a temperature of not less than 2000°C and not more than 3500°C.
藉由滿足上述條件，可以更加適當地促進由於揮發材料的冷凝而形成粒徑相對較小的Mn鐵氧體粒子。再者，可以更加適當地調整所得到的Mn鐵氧體粒子的形狀。再者，可以省略或者簡化後續的製程中的分級等的處理步驟，因而能夠進一步提高Mn鐵氧體粒子的生產率。再者，可以減少在後續的製程中藉由分級而去除的粒子的比例，因而能夠進一步提高Mn鐵氧體粒子的產率。By satisfying the above conditions, the formation of Mn ferrite particles with a relatively small particle size due to condensation of volatile materials can be more appropriately promoted. Furthermore, the shape of the obtained Mn ferrite particles can be adjusted more appropriately. Furthermore, processing steps such as classification in subsequent processes can be omitted or simplified, so the productivity of Mn ferrite particles can be further improved. Furthermore, the proportion of particles removed by classification in subsequent processes can be reduced, thereby further improving the yield of Mn ferrite particles.
接著，將藉由熱噴塗進行主要煅燒所形成的Mn鐵氧體粒子，在大氣中藉由空氣供給而乘於氣流之上進行輸送，使其急速冷卻凝固之後，收集並回收預定的粒徑範圍之Mn鐵氧體粒子。Next, the Mn ferrite particles formed by mainly calcining by thermal spraying are transported in the atmosphere by being supplied with air and riding on the air flow. After rapid cooling and solidification, they are collected and recovered within a predetermined particle size range. Mn ferrite particles.
將急速冷卻凝固的Mn鐵氧體粒子藉由空氣供給而乘於氣流之上進行輸送，粒徑大的粒子在氣流輸送的過程中從氣流落下，而除此以外的其他粒子則被氣流輸送至氣流的下游處，並利用設置於氣流的下游處之旋風分離器及/或過濾器收集預定的粒徑範圍之Mn鐵氧體粒子，藉由此方法可以進行前述收集的步驟。The rapidly cooled and solidified Mn ferrite particles are transported by the air flow by riding on the air flow. The particles with large particle sizes fall from the air flow during the air flow transportation, while the other particles are transported by the air flow. The Mn ferrite particles in a predetermined particle size range are collected by using a cyclone separator and/or filter disposed downstream of the air flow, and the aforementioned collection step can be performed by this method.
藉由將前述氣流輸送時的流速設定為20m/秒以上60m/秒以下，能夠以特別高的選擇性刪選掉粒徑大的粒子，進而能夠更有效率地回收預定的粒徑範圍之Mn鐵氧體粒子。如果流速太小，則連粒徑相對較小的粒子也會在氣流輸送的過程中落下，造成氣流的下游處所回收到的Mn鐵氧體粒子的平均粒徑變得太小，或者，氣流的下游處所回收到的Mn鐵氧體粒子的絕對量變少，導致生產率降低。另一方面，如果流速太大，則連粒徑相對較大的粒子也會被輸送至下游處，造成氣流的下游處所回收到的Mn鐵氧體粒子的平均粒徑會容易變得過大。 之後，可以根據需求對所回收到的Mn鐵氧體粉末進行分類。By setting the flow velocity during the air flow conveyance to 20 m/sec or more and 60 m/sec or less, particles with large particle sizes can be selected out with particularly high selectivity, and Mn in a predetermined particle size range can be recovered more efficiently. ferrite particles. If the flow rate is too small, even relatively small particles will fall during the air flow transportation process, causing the average particle size of the Mn ferrite particles recovered downstream of the air flow to become too small, or the air flow will The absolute amount of Mn ferrite particles recovered at the downstream location becomes smaller, resulting in lower productivity. On the other hand, if the flow rate is too high, even relatively large particles will be transported downstream, causing the average particle size of the Mn ferrite particles recovered downstream of the air flow to easily become too large. Afterwards, the recovered Mn ferrite powder can be sorted according to needs.
《樹脂組合物》 接著，針對本發明的樹脂組合物進行說明。"Resin composition" Next, the resin composition of the present invention will be described.
本發明的樹脂組合物包含前述本發明的粉末和樹脂材料。 藉此，能夠提供適合用於製造電磁波屏蔽性優異的成形體之樹脂組合物。The resin composition of the present invention contains the aforementioned powder of the present invention and a resin material. Thereby, it is possible to provide a resin composition suitable for producing a molded article excellent in electromagnetic wave shielding properties.
作為構成樹脂組合物的樹脂材料，例如，可列舉出環氧樹脂、聚氨酯樹脂、丙烯酸樹脂、矽氧樹脂、各種改性矽氧樹脂（丙烯酸改性、氨基甲酸酯改性、環氧改性、氟）、聚醯胺樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、氟、聚乙烯醇等，可以從以上選擇1種或者組合2種以上使用。Examples of the resin material constituting the resin composition include epoxy resin, polyurethane resin, acrylic resin, silicone resin, and various modified silicone resins (acrylic-modified, urethane-modified, epoxy-modified). , fluorine), polyamide resin, polyimide resin, polyamide imine resin, fluorine, polyvinyl alcohol, etc. You can select one type from the above or use two or more in combination.
再者，樹脂組合物也可以包含本發明的粉末和樹脂材料以外的成分（其他成分）。Furthermore, the resin composition may contain components other than the powder and resin material of the present invention (other components).
作為這種其他成分，例如，可列舉出溶劑、填料（有機填料、無機填料）、增塑劑、抗氧化劑、分散劑、顏料等的著色劑、導熱粒子（導熱係數高的粒子）等。Examples of such other components include solvents, fillers (organic fillers, inorganic fillers), plasticizers, antioxidants, dispersants, colorants such as pigments, thermally conductive particles (particles with high thermal conductivity), and the like.
相對於樹脂組合物中的總固體成分，本發明的粉末的比例（含量）以50質量％以上95質量％以下為佳，且以80質量％以上95質量％以下為較佳。The proportion (content) of the powder of the present invention is preferably 50 mass% or more and 95 mass% or less relative to the total solid content in the resin composition, and is more preferably 80 mass% or more and 95 mass% or less.
藉此，能夠提升本發明的粉末在樹脂組合物中的分散穩定性、樹脂組合物的儲存穩定性、樹脂組合物的成形性等，而且能夠使得使用樹脂組合物所製造出的成形體的機械強度、電磁波的屏蔽性等更加優異。Thereby, the dispersion stability of the powder of the present invention in the resin composition, the storage stability of the resin composition, the moldability of the resin composition, etc. can be improved, and the machine using the molded body produced by the resin composition can be improved. It has superior strength and electromagnetic wave shielding properties.
相對於樹脂組合物中的總固體成分，樹脂材料的比例（含量）以5質量％以上50質量％以下為佳，且以5質量％以上20質量％以下為較佳。The proportion (content) of the resin material is preferably 5 mass% or more and 50 mass% or less, and more preferably 5 mass% or more and 20 mass% or less relative to the total solid content in the resin composition.
藉此，能夠提升本發明的粉末在樹脂組合物中的分散穩定性、樹脂組合物的儲存穩定性、樹脂組合物的成形性等，而且能夠使得使用樹脂組合物所製造出的成形體的機械強度、電磁波的屏蔽性等更加優異。Thereby, the dispersion stability of the powder of the present invention in the resin composition, the storage stability of the resin composition, the moldability of the resin composition, etc. can be improved, and the machine using the molded body produced by the resin composition can be improved. It has superior strength and electromagnetic wave shielding properties.
《成形體》 接著，針對本發明的成形體進行說明。 本發明的成形體，使用包含本發明的粉末和樹脂材料之材料所製造而成。 藉此，能夠提供電磁波的屏蔽性優異之成形體。"Formed Body" Next, the molded article of the present invention will be described. The molded article of the present invention is produced using a material containing the powder of the present invention and a resin material. This makes it possible to provide a molded article having excellent electromagnetic wave shielding properties.
本發明的成形體可以用於任何用途，而以作為電磁波屏蔽材料為佳。 如此一來，可以更顯著地發揮前述根據本發明的效果。The molded article of the present invention can be used for any purpose, but is preferably used as an electromagnetic wave shielding material. In this way, the aforementioned effects according to the present invention can be exerted more significantly.
藉由使用如以上所述的本發明的樹脂組合物，可以適當地製造本發明的成形體。By using the resin composition of the present invention as described above, the molded article of the present invention can be appropriately produced.
作為成形體的成形方法，例如，可列舉出壓縮成型、擠出成型、注塑成型、吹塑（blow）成型、壓延（calendar）成型、各種塗佈方法等。再者，例如，可以藉由在將要形成成形體的部件上直接塗覆樹脂組合物，以形成成形體，或者也可以在單獨製作成形體之後，將其設置於目標的部件（例如，印刷線路基板或金屬箔（例如，銅箔等））上。Examples of the molding method of the molded body include compression molding, extrusion molding, injection molding, blow molding, calendar molding, and various coating methods. Furthermore, for example, the molded body may be formed by directly applying the resin composition to a member to be formed into the molded body, or the molded body may be separately produced and then placed on a target member (for example, a printed circuit). on a substrate or metal foil (e.g., copper foil, etc.)).
另外，根據本發明的粉末，也可以在不進行混合或分散於樹脂等之中並煅燒的步驟之情況下使用，例如，也可以在進行將粉末成形為所需形狀、造粒、塗覆等的步驟之後，進行煅燒（在複合粒子的披覆層不變質的相對低溫之下），以用於製造作為燒結體的成形體。In addition, the powder according to the present invention can also be used without performing the steps of mixing or dispersing it in a resin or the like and calcining it. For example, it can also be used after molding the powder into a desired shape, granulating, coating, etc. After the step, calcination is performed (at a relatively low temperature so that the coating layer of the composite particles does not deteriorate) for producing a shaped body as a sintered body.
另外，本發明的成形體，可以至少一部分包含根據本發明的複合粒子，例如，也可以具有不包含複合粒子的區域。In addition, the molded article of the present invention may contain at least a part of the composite particles according to the present invention, and may, for example, have a region that does not contain the composite particles.
以上，已針對本發明的適當實施形態進行了說明，然而本發明並不限定於此。Suitable embodiments of the present invention have been described above, but the present invention is not limited thereto.
例如，在本發明的複合粒子的製造方法中，除了前述步驟以外，也可以根據需求包括其他步驟（預處理步驟、中間步驟、後處理步驟）。For example, in the method for producing composite particles of the present invention, in addition to the above-mentioned steps, other steps (pretreatment steps, intermediate steps, and post-treatment steps) may be included as required.
再者，本發明的複合粒子，並不限定於藉由前述方法所製造出的複合粒子，也可以是藉由任何方法所製造出的複合粒子。Furthermore, the composite particles of the present invention are not limited to those produced by the above-mentioned method, and may be produced by any method.
再者，在前述實施形態中，已針對將本發明的複合粒子、粉末、樹脂組合物應用於製造電磁波屏蔽材料的情況進行了代表性的說明，然而本發明的複合粒子、粉末、樹脂組合物也可以應用於除了電磁波屏蔽材料以外的製程。例如，本發明的複合粒子、粉末，也可以作為磁芯材料或填料（特別是磁性填料）使用。Furthermore, in the foregoing embodiments, the case where the composite particles, powder, and resin composition of the present invention are applied to the production of electromagnetic wave shielding materials has been representatively described. However, the composite particles, powder, and resin composition of the present invention It can also be applied to processes other than electromagnetic wave shielding materials. For example, the composite particles and powders of the present invention can also be used as magnetic core materials or fillers (especially magnetic fillers).
再者，本發明的複合粒子、粉末，具有可以適當地藉由金屬探測器檢測出的性質。 因此，本發明的複合粒子、粉末、樹脂組合物及成形體，也可以應用於使用金屬探測器進行檢測的目的。Furthermore, the composite particles and powders of the present invention have properties that can be appropriately detected by a metal detector. Therefore, the composite particles, powder, resin composition and molded article of the present invention can also be used for the purpose of detection using a metal detector.
特別是，根據本發明，如以上所述，可以將複合粒子或粉末調整為除了黑色以外的顏色（例如，白色至銀色之間的顏色）。因此，例如，可以將包含複合粒子、粉末的成形體的顏色調整成除了對應於複合粒子、粉末的黑色以外的顏色（例如，白色至銀色之間的顏色），或者藉由使得成形體包含著色劑（包括設置印刷層），可以將成形體調整成所需的顏色。結果，能夠適用於應用在金屬探測器的各種成形體。In particular, according to the present invention, as described above, the composite particles or powder can be adjusted to colors other than black (for example, a color between white and silver). Therefore, for example, the color of a formed body containing composite particles or powder can be adjusted to a color other than black corresponding to the composite particles or powder (for example, a color between white and silver), or by causing the formed body to contain coloring The formed body can be adjusted to the desired color by applying the agent (including setting the printing layer). As a result, it can be applied to various shaped bodies used in metal detectors.
在本發明的成形體應用於金屬探測器的情況下，此成形體也可以具有例如使用除了本發明的樹脂組合物以外的材料所形成的基底部分、和設置在此基底部分的表面上使用本發明的樹脂組合物所形成的表面層。When the molded body of the present invention is applied to a metal detector, the molded body may have, for example, a base portion formed using a material other than the resin composition of the present invention, and may be provided on the surface of the base portion using the base portion. The surface layer formed by the resin composition of the invention.
在本發明的成形體應用於金屬探測器的情況下，此成形體以至少在其表面附近包含複合粒子為佳。 更具體而言，成形體以在厚度方向上距離其表面1.0mm以內的區域中包含複合粒子為佳，且以在厚度方向上距離其表面0.5mm以內的區域中包含複合粒子為較佳。When the molded body of the present invention is used in a metal detector, it is preferable that the molded body contains composite particles at least near its surface. More specifically, the formed body preferably contains composite particles in a region within 1.0 mm from its surface in the thickness direction, and preferably contains composite particles in a region within 0.5 mm from its surface in the thickness direction.
在本發明的成形體應用於金屬探測器的情況下，作為此成形體的用途，例如，可列舉出食品之製造、加工和包裝（包括外箱包裝，以下亦相同）的應用領域、化妝品和準藥品之製造、加工和包裝的應用領域、醫藥品之製造、加工和包裝的應用領域、除了上述以外的產品之製造、加工和包裝的應用領域、醫療應用領域、細胞培養、組織培養、器官培養和基因重組等的進行生物學處理的應用領域、進行化合物的合成等的化學處理的應用領域等。其中，以應用於食品之製造、加工和包裝的領域為佳。When the molded body of the present invention is applied to a metal detector, examples of uses of the molded body include application fields of food manufacturing, processing and packaging (including outer box packaging, the same applies below), cosmetics and Application fields of manufacturing, processing and packaging of quasi-drugs, application fields of manufacturing, processing and packaging of pharmaceuticals, application fields of manufacturing, processing and packaging of products other than the above, medical application fields, cell culture, tissue culture, organs Application fields such as biological processing such as culture and genetic recombination, chemical processing such as compound synthesis, etc. Among them, the fields used in food manufacturing, processing and packaging are preferred.
食品要求具有高安全性，但一般是在容易混入異物的環境中進行製造、加工和包裝。因此，藉由適當地使用將本發明應用於食品之製造、加工和包裝的領域之物品，能夠適當地檢測出此物品的一部分分離的情況、或此物品的至少一部分混入其他物品的情況等。Food requires high safety, but it is generally manufactured, processed and packaged in an environment where foreign matter is easily mixed in. Therefore, by appropriately using an article to which the present invention is applied in the field of manufacturing, processing, and packaging of food, it is possible to appropriately detect the separation of a part of the article or the mixing of at least a part of the article into other articles.
另外，在本說明書中，食品的形態除了固態、半固態（果凍、布丁等的膠狀等）以外，還包括液態，且食品也包括飲料等。再者，食品添加劑和營養補充劑（supplement）（保健品）也包含在食品之中。再者，除了源自動物的肉類、海鮮類、源自植物的蔬菜、水果、種子、穀物、豆類、海藻等天然物及上述的加工產品以外，人工甜味劑、人工調味料等人工的合成物也包含在食品之中。In addition, in this specification, the form of food includes liquid form in addition to solid and semi-solid forms (jelly, pudding, etc., etc.), and food also includes beverages, etc. Furthermore, food additives and nutritional supplements (health products) are also included in food. Furthermore, in addition to animal-derived meat, seafood, plant-derived vegetables, fruits, seeds, grains, beans, seaweed and other natural products and the above-mentioned processed products, artificial sweeteners, artificial seasonings and other artificial synthetic products Objects are also included in food.
用於食品之製造、加工的成形體，例如，可列舉出烹飪設備類、烹飪器具類、烹飪用具類、餐具類、衣物類（人體上穿著的物品）、用於包裝食品的包裝部件、及與上述一併使用的物品、以及用於對上述進行保養（maintenance）、修理等的物品等。Molded articles used in the manufacturing and processing of food, for example, include cooking equipment, cooking utensils, cooking utensils, tableware, clothing (items worn by the human body), packaging parts for packaging food, and Items used together with the above, and items used for maintenance, repair, etc. of the above.
更具體而言，例如，可列舉出加熱板（hot plate）、爐灶、煤氣爐（gas burner）、烤箱（oven）、烤麵包機（toaster）、微波爐、洗碗機、烘碗機、磅秤（scale）、廚房計時器（kitchen timer）、溫度計、淨水器、淨水過濾器（濾芯，cartridge）等的烹飪設備類；鍋、平底鍋（frying pan）、水壺、上述的蓋子、菜刀、剪刀、湯杓（ladle）、抹刀、削皮器（peeler）、切片機（slicer）、攪拌機（mixer）、切碎機（chopper）、搗碎器（masher）、桿麵棍、攪拌器（muddler）、打蛋器、網篩、碗（bowl）、瀝水器、砧板、地墊（mat）、飯匙、模具、模切、去浮沫杓、磨碎機（食品分級機，food grader）、鍋鏟（turner）、插籤（pick）、篩子、研磨機(mill)、鍋內蓋、製冰盒、燒烤網、夾子(tong)、切蛋器、量杯、量匙等的烹飪器具類；抹布、廚房紙巾(kitchen paper)、手帕、毛巾(towel)、紙巾、排水板(sheet)、保鮮膜(wrap film)、烘焙紙(oven paper)、擠壓袋、鍋架、鍋墊等的烹飪用具類；盤子、杯子(cup)、碗、筷子(包括公筷)、湯匙(spoon)、叉子(fork)、刀子(knife)、甲殼類動物的腿部足部之取出器具(蟹鉗(crab spoon)、蟹叉(crab fork))等的餐具類；圍裙(apron)、白大衣、面具(mask)、手套、鞋子、襪子、內衣、帽子、眼鏡等的衣物類(人體上穿著的物品)；用於食品的層壓膜(laminated film)等的食品用包裝部件、包裝用管材(tube)、食品用儲存瓶(bottle)、塑料密封容器等的食品包裝部件；其他、瀝乾網、水槽管(hose)、砧板架、餐具架、海綿(sponge)、鋼刷、洗劑容器、磨刀石、磨刀器(sharpener)、或上述的構成部件，然而並不限定於此。 More specifically, for example, a hot plate, a stove, a gas burner, an oven, a toaster, a microwave oven, a dishwasher, a dish dryer, a scale ( cooking equipment such as scale, kitchen timer, thermometer, water purifier, water purification filter (cartridge); pots, frying pans, kettles, lids as mentioned above, kitchen knives, scissors , ladle, spatula, peeler, slicer, mixer, chopper, masher, stick, muddler ), egg beater, mesh sieve, bowl (bowl), drainer, chopping board, floor mat (mat), rice spoon, mold, die cutting, defloating ladle, grater (food grader), Cooking utensils such as turners, picks, sieves, mills, pot lids, ice boxes, barbecue nets, tongs, egg cutters, measuring cups, measuring spoons, etc.; Cooking rags, kitchen paper, handkerchiefs, towels, paper towels, drainage sheets, wrap film, oven paper, squeeze bags, pot holders, pot holders, etc. Utensils; plates, cups, bowls, chopsticks (including serving chopsticks), spoons, forks, knives, tools for removing crustacean legs and feet (crab claws) Tableware such as spoon, crab fork); clothing (articles worn on the human body) such as aprons, white coats, masks, gloves, shoes, socks, underwear, hats, glasses, etc. ; Food packaging components such as laminated films for food, packaging tubes, food storage bottles, plastic sealed containers, etc.; Others, drain nets, sinks However, it is not limited to a hose, a cutting board holder, a cutlery holder, a sponge, a steel brush, a detergent container, a whetstone, a sharpener, or the above components.
以下，基於實施例及比較例詳細說明地本發明，然而本發明並不限定於此。在以下的說明中，對於未提及溫度條件的處理、測量，係在室溫(25℃)下進行。 Hereinafter, the present invention will be described in detail based on Examples and Comparative Examples, but the present invention is not limited thereto. In the following description, processing and measurement where temperature conditions are not mentioned are performed at room temperature (25°C).
《1》複合粒子、粉末的製造 《1》Manufacturing of composite particles and powders
如以下所述製造各實施例及各比較例的複合粒子、粉末。 The composite particles and powders of each Example and each Comparative Example were produced as follows.
(實施例1) (Example 1)
首先，將作為原料的Fe2O3及Mn3O4以預定的比例混合，並用亨舍爾攪拌機(Henschel mixer)混合15分鐘。 First, Fe 2 O 3 and Mn 3 O 4 as raw materials were mixed in a predetermined ratio and mixed for 15 minutes using a Henschel mixer.
將以上所得到的混合物使用乾式造粒機(roller compactor)加以造粒化之後，使用旋轉窯(rotary kiln)在空氣中以1000℃進行5小時的預煅燒。 The mixture obtained above was granulated using a dry granulator (roller compactor), and then preliminarily calcined in the air at 1000° C. for 5 hours using a rotary kiln.
在進行預煅燒之後，使用球磨機(ball mill)粉碎，得到體積平均粒徑為1.8μm的粉末狀的預煅燒體（煅燒粉末）。After preliminary calcination, it was pulverized using a ball mill to obtain a powdery preliminary calcination body (calcined powder) with a volume average particle diameter of 1.8 μm.
接著，使用所得到的粉末狀的預煅燒體，在丙烷：氧氣=10Nm3 /hr：35Nm3 /hr之可燃性氣體的燃燒火焰中，以流速為40m/秒的條件進行熱噴塗。此時，由於在將造粒物連續地流動的同時進行熱噴塗，因此使得熱噴塗和淬火後的粒子是獨立的，而不會彼此結合。之後，藉由設置在氣流的下游側之旋風分離器，將冷卻的粒子回收。如此一來，可得到由複數個Mn鐵氧體粒子所構成的鐵氧體粉末（Mn鐵氧體粉末）（體積平均粒徑：27.5μm）。對所得到的鐵氧體粉末進行氣流分級，以得到體積平均粒徑為4.7μm。Next, the obtained powdery pre-calcined body was thermally sprayed in a combustion flame of a combustible gas of propane: oxygen = 10 Nm 3 /hr: 35 Nm 3 /hr at a flow rate of 40 m/sec. At this time, since thermal spraying is performed while continuously flowing the granulated material, the particles after thermal spraying and quenching are independent and do not combine with each other. Afterwards, the cooled particles are recovered through a cyclone separator installed on the downstream side of the air flow. In this way, ferrite powder (Mn ferrite powder) composed of a plurality of Mn ferrite particles (volume average particle diameter: 27.5 μm) can be obtained. The obtained ferrite powder was air-flow classified to obtain a volume average particle size of 4.7 μm.
另外，粉末的體積平均粒徑可藉由以下所述的測量方法求得。亦即，首先，將10g作為樣品的粉末和80ml的水置於100ml的燒杯中，並加入2滴分散劑（六偏磷酸鈉）。然後，使用超音波均化器（homogenizer）（由SMT股份有限公司所製造的的UH-150型）進行分散。此時，超音波均化器的輸出程度設定為4，並進行20秒的分散。之後，去除形成於燒杯表面上的泡沫，並引入雷射衍射型粒度分佈測量裝置（由島津製作所製造的SALD-7500 nano）以進行測量。此時的測量條件為泵速為7，折射率為1.70-0.50i，且內部超音波照射時間為30。另外，對於後續描述的其他實施例及比較例，也以相同的方式求得。In addition, the volume average particle diameter of the powder can be determined by the measurement method described below. That is, first, 10 g of powder as a sample and 80 ml of water are placed in a 100 ml beaker, and 2 drops of dispersant (sodium hexametaphosphate) are added. Then, an ultrasonic homogenizer (UH-150 model manufactured by SMT Co., Ltd.) was used for dispersion. At this time, the output level of the ultrasonic homogenizer was set to 4, and dispersion was performed for 20 seconds. After that, the foam formed on the surface of the beaker was removed, and a laser diffraction type particle size distribution measuring device (SALD-7500 nano manufactured by Shimadzu Corporation) was introduced for measurement. The measurement conditions at this time are that the pump speed is 7, the refractive index is 1.70-0.50i, and the internal ultrasonic irradiation time is 30. In addition, other Examples and Comparative Examples described later are also obtained in the same manner.
再者，鐵氧體粉末的SF-1的平均值為106。Furthermore, the average value of SF-1 of the ferrite powder is 106.
可如以下所述求得形狀係數SF-1。 亦即，首先，使用掃描電子顯微鏡（FE-SEM（SU-8020，由日立先端科技公司所製造））及能量色散型X射線分析裝置（EDX）（由堀場製作所所製造的E-MAX），將放大倍率設定為1000倍，並使用EDX附帶的功能之粒子分析功能，自動測量1000個以上的粒子之等效圓直徑、圓周、長度、寬度、面積。The shape coefficient SF-1 can be obtained as follows. That is, first, using a scanning electron microscope (FE-SEM (SU-8020, manufactured by Hitachi Advanced Technologies Co., Ltd.)) and an energy dispersive X-ray analyzer (EDX) (E-MAX manufactured by Horiba Manufacturing Co., Ltd.), Set the magnification to 1000 times and use the particle analysis function that comes with EDX to automatically measure the equivalent circle diameter, circumference, length, width, and area of more than 1000 particles.
在所得到的數據中，明顯彼此重疊的粒子（圓周長度為從等效圓直徑所計算出的圓周長度的1.8倍以上的粒子），除了細粉末（等效圓直徑比1μm更小的粉末）以外，將粒子的最大長度（水平費雷特徑）設為R，面積設為投影面積S，以上述式計算出SF-1的值。In the obtained data, particles that clearly overlap each other (particles whose circumferential length is more than 1.8 times the circumferential length calculated from the equivalent circle diameter), except for fine powders (powders with an equivalent circle diameter smaller than 1 μm) In addition, assuming that the maximum length of the particle (horizontal Feret diameter) is R and the area is the projected area S, the value of SF-1 is calculated using the above formula.
計算每個粒子的SF-1，採用200個以上粒子的平均值定義為鐵氧體粉末的SF-1。另外，對於後續描述的其他實施例及比較例，也以相同的方式求得。Calculate the SF-1 of each particle, and use the average value of more than 200 particles to define the SF-1 of the ferrite powder. In addition, other Examples and Comparative Examples described later are also obtained in the same manner.
再者，所得到的鐵氧體粉末的BET比表面積為0.68m2 /g。 可藉由使用比表面積測量裝置（型號：Macsorb HM model-1208（由MOUNTECH公司所製造））進行測量，以求得BET比表面積。更具體而言，將大約5g的測量樣品放入專用於比表面積測量裝置的標準樣本池（sample cell）中，用精密天平精確地秤量重量，並將樣品（鐵氧體粉末）放置於測量點，以開始測量。利用單點法進行測量且在測量結束時輸入樣品的重量，則會自動計算出BET比表面積。另外，作為測量前的預處理，在藥品包裝紙上量取出大約20g的測量樣品之後，利用真空乾燥機脫氣至-0.1MPa，並在確認真空度達到-0.1MPa以下之後，將其在200℃下加熱2小時。測量環境設定為不會冷凝的條件，溫度：10～30℃，濕度：相對濕度為20～80％。Furthermore, the BET specific surface area of the obtained ferrite powder was 0.68 m 2 /g. The BET specific surface area can be obtained by measuring using a specific surface area measuring device (model: Macsorb HM model-1208 (manufactured by MOUNTECH)). More specifically, approximately 5 g of the measurement sample is placed into a standard sample cell (sample cell) dedicated to a specific surface area measurement device, the weight is accurately weighed with a precision balance, and the sample (ferrite powder) is placed at the measurement point , to start measuring. When measuring using the single point method and entering the weight of the sample at the end of the measurement, the BET specific surface area will be automatically calculated. In addition, as a pretreatment before measurement, after measuring about 20g of the measurement sample on the drug packaging paper, use a vacuum dryer to degas to -0.1MPa, and after confirming that the vacuum degree is below -0.1MPa, heat it at 200°C Heat for 2 hours. The measurement environment is set to non-condensing conditions, temperature: 10~30°C, humidity: relative humidity 20~80%.
再者，關於鐵氧體粉末，使用振動樣品型磁性測量裝置進行測量，可得知飽和磁化強度為87.1emu/g，剩餘磁化強度為2.8emu/g，保磁力為42Oe。Furthermore, when ferrite powder was measured using a vibrating sample type magnetic measuring device, it was found that the saturation magnetization was 87.1 emu/g, the residual magnetization was 2.8 emu/g, and the coercive force was 42 Oe.
可以如下列所述求得上述的磁性特性。亦即，首先，將內徑為5mm、高度為2mm的電池填充待測量的鐵氧體粉末，並放置於振動樣品型磁性測量裝置（由東英工業公司所製造的VSM-C7-10A）之中。接著，施加磁場並掃描至5kOe，然後減少施加的磁場，以產生遲滯曲線。之後，根據此曲線的數據，求出關於鐵氧體粉末的飽和磁化強度、剩餘磁化強度及保磁力。另外，關於作為後續描述的複合粒子的聚集體之粉末，也以相同的方式求得磁性特性。再者，對於後續描述的其他實施例及比較例，也以相同的方式求得。The above-mentioned magnetic properties can be obtained as follows. That is, first, a battery with an inner diameter of 5 mm and a height of 2 mm is filled with ferrite powder to be measured and placed on a vibrating sample type magnetic measurement device (VSM-C7-10A manufactured by Dongying Industrial Co., Ltd.) middle. Next, a magnetic field is applied and swept to 5 kOe, then the applied magnetic field is reduced to produce a hysteresis curve. Then, based on the data of this curve, the saturation magnetization, residual magnetization, and coercive force of the ferrite powder are obtained. In addition, the magnetic properties were also obtained in the same manner for the powder that is an aggregate of composite particles described later. In addition, other Examples and Comparative Examples described later are also obtained in the same manner.
秤量0.2g所得到的鐵氧體粉末，在60ml的純水中加入20ml的1N的鹽酸以及20ml的1N的硝酸並進行加熱，製備出鐵氧體粉末完全溶解的水溶液，藉由使用ICP分析裝置（由島津製作所製造的ICPS-1000IV）進行測量，求得Fe、Mn、Mg及Sr的含量。再者，對於後續描述的其他實施例及比較例，也以相同的方式求得。Weigh 0.2g of the obtained ferrite powder, add 20ml of 1N hydrochloric acid and 20ml of 1N nitric acid to 60ml of pure water, and heat to prepare an aqueous solution in which the ferrite powder is completely dissolved. By using an ICP analysis device (ICPS-1000IV manufactured by Shimadzu Corporation) was measured to determine the contents of Fe, Mn, Mg and Sr. In addition, other Examples and Comparative Examples described later are also obtained in the same manner.
之後，藉由對所得到的鐵氧體粉末進行無電鍍，以得到在由Mn鐵氧體所構成的母粒子的表面上包含複數個具有由Ag所構成的披覆層的複合粒子之粉末。Thereafter, the obtained ferrite powder is electroless plated to obtain a powder including a plurality of composite particles having a coating layer composed of Ag on the surface of a mother particle composed of Mn ferrite.
（實施例2、3） 在作為母粒子使用的Mn鐵氧體粒子（鐵氧體粉末）的製造過程中，除了藉由調整原料的比例、預煅燒的條件、熱噴塗處理條件、分級條件的同時，也調整披覆層的形成條件，使得粉末（複數個複合粒子的聚集體）的條件如表1、表2所示以外，其餘以與前述實施例1相同的方式製造出粉末（複數個複合粒子的聚集體）。(Examples 2 and 3) In the manufacturing process of Mn ferrite particles (ferrite powder) used as mother particles, in addition to adjusting the ratio of raw materials, pre-calcination conditions, thermal spray treatment conditions, and classification conditions, the coating layer is also adjusted The powder (aggregate of multiple composite particles) was produced in the same manner as in Example 1 except that the conditions for forming the powder (aggregate of multiple composite particles) were as shown in Table 1 and Table 2.
（比較例1） 在本比較例中，將包含複數個由Mn-Mg-Sr類鐵氧體所構成的粒子的聚集體，直接作為目標的粉末使用。亦即，構成本比較例的粉末之粒子由Mn-Mg-Sr類鐵氧體所構成，而並沒有設置披覆層。(Comparative example 1) In this comparative example, an aggregate containing a plurality of particles composed of Mn-Mg-Sr-based ferrite is used as the target powder. That is, the particles constituting the powder of this comparative example are composed of Mn-Mg-Sr ferrite, and no coating layer is provided.
（比較例2） 除了使用由Mn-Mg-Sr類鐵氧體所構成的粒子取代由Mn鐵氧體所構成的粒子作為母粒子以外，其餘以與前述實施例1相同的方式製造出粉末。亦即，在本比較例中，構成粉末之複合粒子具有由Mn-Mg-Sr類鐵氧體所構成的母粒子、和設置於其表面上由Ag所構成的披覆層。(Comparative example 2) Powder was produced in the same manner as in Example 1 except that particles composed of Mn-Mg-Sr ferrite were used as the mother particles instead of particles composed of Mn ferrite. That is, in this comparative example, the composite particles constituting the powder have mother particles composed of Mn-Mg-Sr ferrite and a coating layer composed of Ag provided on the surface thereof.
（比較例3） 除了省略在鐵氧體粉末上形成披覆層以外，其餘以與前述實施例1相同的方式製造出粉末。亦即，在本比較例中，將鐵氧體粉末直接作為目標的粉末使用。(Comparative example 3) The powder was produced in the same manner as in Example 1 except that forming a coating layer on the ferrite powder was omitted. That is, in this comparative example, ferrite powder is used as it is as the target powder.
前述各實施例及各比較例的粉末的成分統整於表1、表2中。 另外，相對於前述各實施例的粉末的顏色為白色至銀色之間的顏色，比較例1、3的粉末的顏色為黑色。The ingredients of the powders of each of the aforementioned examples and comparative examples are summarized in Table 1 and Table 2. In addition, while the color of the powder of each of the above-described examples is between white and silver, the color of the powder of Comparative Examples 1 and 3 is black.
再者，在前述各實施例及比較例2中，母粒子中除了鐵氧體以外的成分的含量為0.1質量％以下。In addition, in each of the above-described Examples and Comparative Example 2, the content of components other than ferrite in the mother particles was 0.1% by mass or less.
再者，在前述各實施例及比較例2中，披覆層中除了Ag以外的成分的含量為0.1質量％以下。藉由使用螢光X射線的測量方法來求得披覆層中Ag的含量。亦即，將100質量份的鐵氧體粒子作為母粒子，將Ag粉末以0.1質量份、0.5質量份、1質量份的比例，利用球磨機（100rpm）混合30分鐘之後，使用螢光X射線測量裝置（由理學（Rigaku）有限公司所製造的ZSX100s），測量Ag的強度以製作校準曲線，然後對前述各實施例及比較例2的粉末（複數個複合粒子的聚集體），使用螢光X射線測量裝置測量Ag的強度，並計算出Ag的含量。Furthermore, in each of the above-described Examples and Comparative Example 2, the content of components other than Ag in the coating layer was 0.1% by mass or less. The Ag content in the coating layer is determined by using fluorescence X-ray measurement. That is, 100 parts by mass of ferrite particles were used as mother particles, and Ag powder was mixed in a ratio of 0.1 part by mass, 0.5 part by mass, and 1 part by mass using a ball mill (100 rpm) for 30 minutes, and then measured using fluorescent X-rays. The device (ZSX100s manufactured by Rigaku Co., Ltd.) measured the intensity of Ag to prepare a calibration curve, and then used fluorescent The radiation measuring device measures the intensity of Ag and calculates the Ag content.
再者，在前述各實施例及比較例2中，粉末中除了前述複合粒子以外的成分的含量為0.1質量％以下。Furthermore, in each of the above-described Examples and Comparative Example 2, the content of components other than the composite particles in the powder was 0.1% by mass or less.
再者，藉由與前述鐵氧體粉末相同的測量方法，求出前述各實施例及各比較例的粉末整體的體積平均粒徑、磁性特性、SF-1的值。Furthermore, the volume average particle diameter, magnetic properties, and SF-1 value of the entire powder of each of the above-described Examples and Comparative Examples were determined by the same measurement method as the above-described ferrite powder.
再者，根據JIS R1628，使用USP振實密度測量裝置（粉末測試儀PT-X，由細川密克朗公司所製造），測量出振實密度。In addition, in accordance with JIS R1628, the tap density was measured using a USP tap density measuring device (Powder Tester PT-X, manufactured by Hosokawa Micron Corporation).
再者，根據JIS Z 8807：2012，使用MUNTECH公司所製造的全自動真密度測量裝置Macpycno，測量出真密度。 分別藉由上述的方法測量出表1中的居禮溫度、披覆層的厚度T。Furthermore, in accordance with JIS Z 8807:2012, the true density is measured using the fully automatic true density measuring device Macpycno manufactured by MUNTECH. The Curie temperature and the thickness T of the coating layer in Table 1 were measured by the above methods respectively.
再者，圖1繪示出實施例1的複合粒子的SEM剖面圖，圖2繪示出實施例2的複合粒子的SEM剖面圖，且圖3繪示出實施例3的複合粒子的SEM剖面圖。Furthermore, Figure 1 shows a SEM cross-section of the composite particles of Example 1, Figure 2 shows a SEM cross-section of the composite particles of Example 2, and Figure 3 shows a SEM cross-section of the composite particles of Example 3. Figure.
[表1] [Table 1]
[表2] [Table 2]
《2》藉由KEC方法評價電磁波屏蔽能力 分別秤量出70質量份的在前述各實施例及各比較例中所得到的粉末和使得黏合劑樹脂（PVA）為30質量份的固體成分之10質量％的PVA水溶液，並利用自轉公轉混合裝置進行5分鐘的分散和混合。《2》Evaluation of electromagnetic wave shielding ability by KEC method 70 parts by mass of the powder obtained in each of the above-mentioned examples and each comparative example and a 10% by mass PVA aqueous solution such that the binder resin (PVA) has a solid content of 30 parts by mass were weighed out, and a rotation-revolution mixing device was used. Allow 5 minutes for dispersing and mixing.
將所得到的混合溶液倒入模塑用的模具中，並使水分蒸發，以得到厚度為1mm的片狀模塑體。The obtained mixed solution was poured into a mold for molding, and the water was evaporated to obtain a sheet-shaped molded body with a thickness of 1 mm.
利用KEC法，測量出所得到的片狀模塑體的磁場的電磁波屏蔽能力（衰減率）。另外，在0.1MHz～1GHz的範圍內，進行磁場的電磁波屏蔽能力（衰減率）的測量。The electromagnetic wave shielding ability (attenuation rate) of the magnetic field of the obtained sheet-shaped molded body was measured using the KEC method. In addition, the electromagnetic wave shielding ability (attenuation rate) of the magnetic field is measured in the range of 0.1MHz to 1GHz.
《3》電阻率 使用在前述各實施例及各比較例中所得到的粉末，如以下所述進行對於電阻率的評價。《3》Resistivity The resistivity was evaluated as follows using the powder obtained in each of the above-described Examples and Comparative Examples.
首先，在剖面面積為4cm2 的氟樹脂製成之圓筒（cylinder）內填充出高度為4mm的粉末作為樣品之後，在兩端連接電極，並在其上放置1kg的重物，以測量出電阻。電阻的測量係利用Keithley公司所製造的2182A型奈米伏特計，施加1V的測量電壓並測量經過60秒之後的阻抗，以計算出體積電阻。First, after filling a cylinder (cylinder) made of fluororesin with a cross-sectional area of 4cm2 with a height of 4mm as a sample, electrodes are connected to both ends and a 1kg weight is placed on them to measure resistance. The resistance was measured using a 2182A nanovoltmeter manufactured by Keithley Company, applying a measurement voltage of 1V and measuring the impedance after 60 seconds to calculate the volume resistance.
對於各實施例及各比較例，藉由KEC方法的電磁波屏蔽效果的評價結果顯示於圖4，而電阻率的結果顯示於表3。For each Example and each Comparative Example, the evaluation results of the electromagnetic wave shielding effect by the KEC method are shown in Figure 4, and the results of the resistivity are shown in Table 3.
[表3]
從圖4中明顯得知，可以確認在本發明中，電磁波屏蔽能力（衰減率）的頻率依賴性根據披覆層的厚度轉移到低頻側，也確認了由於Mn鐵氧體粒子（母粒子）表面上存在金屬披覆膜（披覆層）因而屏蔽了電磁波，相對於此，在比較例1、3中，由於沒有金屬披覆層，因此沒有得到令人滿意的結果。再者，在比較例2中，不僅電磁波屏蔽能力的上升轉移到高頻側，而且電磁波屏蔽能力的結果也比實施例1更差。 [產業上的可利性]As is evident from Figure 4, it was confirmed that in the present invention, the frequency dependence of the electromagnetic wave shielding ability (attenuation rate) shifts to the low frequency side depending on the thickness of the coating layer, and it was also confirmed that the Mn ferrite particles (mother particles) In contrast, in Comparative Examples 1 and 3, satisfactory results were not obtained because there was no metal coating layer on the surface, thereby shielding electromagnetic waves. Furthermore, in Comparative Example 2, not only did the increase in the electromagnetic wave shielding ability shift to the high-frequency side, but the result of the electromagnetic wave shielding ability was also worse than in Example 1. [Industrial profitability]
本發明能夠提供電磁波的屏蔽性優異之複合粒子、粉末，也提供電磁波的屏蔽性優異之成形體，而且還提供可適用於製造前述成形體的樹脂組合物。The present invention can provide composite particles and powders excellent in electromagnetic wave shielding properties, a molded article excellent in electromagnetic wave shielding properties, and a resin composition suitable for producing the molded articles.
雖然已經參照特定的實施例詳細地說明了本發明，然而對於本領域技術人員來說顯而易見的是在不脫離本發明的精神和範圍的情況下可以進行各種變更和修改。 本申請以2018年2月13日在日本提出申請的日本專利申請（專利申請第2018-023566號）作為基礎，並將其內容引用於此。Although the present invention has been described in detail with reference to specific embodiments, it is obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2018-023566) filed in Japan on February 13, 2018, the content of which is incorporated herein by reference.
無。without.
[圖1]係實施例1的複合粒子之SEM剖面圖。 [圖2]係實施例2的複合粒子之SEM剖面圖。 [圖3]係實施例3的複合粒子之SEM剖面圖。 [圖4]係藉由KEC法評價電磁波屏蔽效果的結果之曲線圖。[Fig. 1] is an SEM cross-sectional view of the composite particles of Example 1. [Fig. 2] is an SEM cross-sectional view of the composite particles of Example 2. [Fig. 3] is an SEM cross-sectional view of the composite particles of Example 3. [Figure 4] is a graph showing the results of evaluating the electromagnetic wave shielding effect by the KEC method.
無。without.
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| ??PCT/JP2019/004303 | 2019-02-06 | ||
| PCT/JP2019/004303 WO2019159799A1 (en) | 2018-02-13 | 2019-02-06 | Composite particle, powder, resin composition, and molded article |
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| TW202124285A (en) * | 2019-10-07 | 2021-07-01 | 日商保德科技股份有限公司 | Ferrite powder, ferrite resin composite material, and electromagnetic shielding material, electronic material, or electronic component |
| KR20220130130A (en) * | 2020-01-24 | 2022-09-26 | 파우더테크 컴퍼니 리미티드 | Ferrite powder and its manufacturing method |
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| KR20070097626A (en) * | 2006-03-28 | 2007-10-05 | 신경자 | Primer paint for electromagnetic waves sheild and extiction, and its manufacturing method |
| TW201630817A (en) * | 2015-01-28 | 2016-09-01 | Powdertech Co Ltd | Magnetic filler |
| CN107275023A (en) * | 2016-04-08 | 2017-10-20 | 中国人民解放军国防科学技术大学 | Golden shell magnetic bead and its preparation method and application |
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| EP3504765A1 (en) * | 2016-08-26 | 2019-07-03 | NuCurrent, Inc. | Wireless connector system |
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| TW201630817A (en) * | 2015-01-28 | 2016-09-01 | Powdertech Co Ltd | Magnetic filler |
| CN107275023A (en) * | 2016-04-08 | 2017-10-20 | 中国人民解放军国防科学技术大学 | Golden shell magnetic bead and its preparation method and application |
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