JPH10324510A - Aluminum nitride powder and its production - Google Patents
Aluminum nitride powder and its productionInfo
- Publication number
- JPH10324510A JPH10324510A JP9133111A JP13311197A JPH10324510A JP H10324510 A JPH10324510 A JP H10324510A JP 9133111 A JP9133111 A JP 9133111A JP 13311197 A JP13311197 A JP 13311197A JP H10324510 A JPH10324510 A JP H10324510A
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- Prior art keywords
- aluminum nitride
- nitride powder
- water
- fluidity
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Ceramic Products (AREA)
- Glanulating (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、流動性及び耐水性
に優れ、イオン性成分の溶出性の低い窒化アルミニウム
粉末及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum nitride powder having excellent fluidity and water resistance and low elution of ionic components, and a method for producing the same.
【０００２】[0002]
【従来の技術】窒化アルミニウム粉末は熱伝導性、機械
的強度及び電気絶縁性に優れた特性を持った物質として
知られており、構造用材料、機能用材料等多方面に使用
されつつある。しかし、同時に窒化アルミニウム粉末は
加水分解しやすいという性質も有しており、大気中の水
分でさえも容易に分解し、下記（１）式に従って水酸化
アルミニウムとアンモニアを生成し、窒化アルミニウム
粉末の特性を失ってしまうという問題点がある。2. Description of the Related Art Aluminum nitride powder is known as a substance having excellent properties of thermal conductivity, mechanical strength and electrical insulation, and is being used in various fields such as structural materials and functional materials. However, at the same time, the aluminum nitride powder has a property that it is easily hydrolyzed, and even the moisture in the atmosphere is easily decomposed, and aluminum hydroxide and ammonia are generated according to the following formula (1). There is a problem that characteristics are lost.
【０００３】 ＡｌＮ＋３Ｈ２Ｏ→Ａｌ（ＯＨ）３＋ＮＨ３ ・・・・・ （１） 従って、高温用炉材等の構造用材料として使用する際、
成形時に使用するバインダーが水系の場合、加水分解し
窒化アルミニウム粉末の本来の特性を失うため、引火、
発火性、かつ有害な有機溶剤を使用せざるを得ない。ま
た、白板、メタライズ基板等の機能材料も加水分解によ
る性能劣化が問題となる。また、半導体デバイス、ＩＣ
等の半導体素子はパッケージで外部より保護されてい
る。そのパッケージに、高分子材料が使用されており、
高分子材料自身は熱伝導性が低いため、半導体素子を使
用した回路から発生した熱を外部に放散・除去を行うた
め、熱伝導性に優れた無機微粒子（シリカ、窒化ほう
素、窒化アルミニウム等）を樹脂用のフィラーとして使
用している。近年、より高い熱伝導性を有する窒化アル
ミニウムがフィラーとして用いられるようになってき
た。樹脂用のフィラーとして使用した場合も大気中の水
分がフィルムを透過し、窒化アルミニウム粉末が加水分
解を受けて、熱伝導性の低下や樹脂の劣化をもたらす。
このように上記用途に窒化アルミニウム粉末を使用する
際には、加水分解の進行を抑制する性質（以下、耐水性
と記す）を付与する必要がある。AlN + 3H 2 O → Al (OH) 3 + NH 3 (1) Therefore, when used as a structural material such as a high-temperature furnace material,
If the binder used during molding is water-based, it will hydrolyze and lose the original properties of aluminum nitride powder,
The use of flammable and harmful organic solvents has to be used. Also, functional materials such as a white plate and a metallized substrate have a problem of performance degradation due to hydrolysis. Semiconductor devices, IC
Are protected from the outside by a package. A polymer material is used for the package,
Since the polymer material itself has low thermal conductivity, it dissipates and removes the heat generated from the circuit using the semiconductor element to the outside. Therefore, inorganic particles with excellent thermal conductivity (silica, boron nitride, aluminum nitride ) Is used as a resin filler. In recent years, aluminum nitride having higher thermal conductivity has been used as a filler. Also when used as a resin filler, moisture in the atmosphere permeates the film and the aluminum nitride powder undergoes hydrolysis, resulting in a decrease in thermal conductivity and deterioration of the resin.
As described above, when the aluminum nitride powder is used for the above purpose, it is necessary to impart a property of suppressing the progress of hydrolysis (hereinafter, referred to as water resistance).
【０００４】そこで従来から窒化アルミニウム粉末に耐
水性を付与する検討がなされている。例えば、窒化アル
ミニウム粉末の表面被覆剤に重合性モノマーを使用する
方法（特開平１−１７９７１１号公報）、有機系珪素カ
ップリング剤を使用し、シロキサン結合を有するもの
（特開平７−３３４１５号公報）、ヒドロキシル基、ア
ミン基、カルボキシル基によるもの（特開平３−２６１
６６５号公報、特開平６−３４５５３８号公報）、また
窒化アルミニウム粉末を若干の酸素を含む雰囲気で焼成
することによるα−アルミナを形成したもの（特開平４
−１７５２０９号公報）等が開示されている。しかしな
がらこれらの方法では、充分な耐水性を得ることができ
ない。Therefore, studies have been made to impart water resistance to aluminum nitride powder. For example, a method in which a polymerizable monomer is used as a surface coating agent for aluminum nitride powder (JP-A-1-179711), a method using an organic silicon coupling agent and having a siloxane bond (JP-A-7-33415). ), A hydroxyl group, an amine group or a carboxyl group (JP-A-3-261)
No. 665, JP-A-6-345538), and a product in which α-alumina is formed by firing aluminum nitride powder in an atmosphere containing some oxygen (Japanese Patent Laid-Open No.
-175209) and the like. However, these methods cannot provide sufficient water resistance.
【０００５】本発明者らは水の存在下で窒化アルミニウ
ム粉末を燐酸化合物で処理し、特定量の燐酸化合物を窒
化アルミニウム表面に含有させることにより、優れた耐
水性を有する窒化アルミニウム粉末を得ることができた
（特願平８−１１３７１号公報、特願平８−２８６７８
０号公報）。しかし、多方面で更に高い耐水性を有する
窒化アルミニウム粉末が求められると同時に、溶出する
イオン性成分の低減の要望もある。The present inventors have obtained an aluminum nitride powder having excellent water resistance by treating an aluminum nitride powder with a phosphate compound in the presence of water and allowing a specific amount of the phosphate compound to be contained on the aluminum nitride surface. (Japanese Patent Application Nos. 8-111371 and 8-28678).
No. 0). However, aluminum nitride powders having higher water resistance in various fields are required, and at the same time, there is a demand for reduction of ionic components eluted.
【０００６】また、特願平８−２８６７８０号公報記載
の方法で優れた耐水性が得られるが、燐酸化合物による
処理により表面状態が変化し、未処理のものと比べると
流動性が著しく低下してしまう。そのため、耐水性窒化
アルミニウムは流動性が悪いために、樹脂との混練時、
窒化アルミニウム粉末が凝集体を形成し樹脂に均一に分
散させることが困難である。例えば、そのため、窒化ア
ルミニウム粉末を樹脂と混練する際、篩で分級しながら
混練することが必要となり、工程が増えコストアップに
つながっている。Although excellent water resistance can be obtained by the method described in Japanese Patent Application No. 8-286780, the surface condition is changed by the treatment with a phosphoric acid compound, and the fluidity is significantly reduced as compared with the untreated one. Would. Therefore, when water-resistant aluminum nitride has poor fluidity, when kneading with resin,
It is difficult for the aluminum nitride powder to form an aggregate and be uniformly dispersed in the resin. For example, when kneading an aluminum nitride powder with a resin, it is necessary to knead the aluminum nitride powder while classifying it with a sieve, which increases the number of steps and leads to an increase in cost.
【０００７】[0007]
【発明が解決しようとする課題】本発明の目的は更に
優れた耐水性の付与イオン性成分の溶出の抑制優れ
た流動性の付与にある。SUMMARY OF THE INVENTION It is an object of the present invention to provide excellent water resistance, to suppress elution of ionic components, and to provide excellent fluidity.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、鋭意検討
を重ねた結果、窒化アルミニウム粉末の表面に特定量の
燐酸化合物を有する窒化アルミニウムが優れた耐水性を
有することを知見し、更に検討した結果、特定量の燐酸
化合物を窒化アルミニウム粉末の表面に含有させ且つ、
特定の流動性改良剤を含有させることにより、更に優
れた耐水性の付与イオン性成分の溶出の抑制優れた
流動性の付与という目的を達成できることを見い出し、
本発明を完成させるに至った。Means for Solving the Problems As a result of intensive studies, the present inventors have found that aluminum nitride having a specific amount of a phosphoric acid compound on the surface of aluminum nitride powder has excellent water resistance. As a result of the examination, a specific amount of a phosphoric acid compound is contained on the surface of the aluminum nitride powder, and
By adding a specific fluidity improver, it has been found that the objective of imparting excellent fluidity can be achieved by suppressing the dissolution of ionic components, which imparts more excellent water resistance,
The present invention has been completed.
【０００９】即ち、本発明は流動性改良剤を含有し、且
つ燐酸化合物で処理された窒化アルミニウム粉末であっ
て、該窒化アルミニウム粉末に対して該燐酸化合物がＰ
２Ｏ ５換算で０．１〜１０重量％含有することを特徴と
する流動性及び耐水性に優れ、イオン性成分の溶出性の
低い窒化アルミニウム粉末、及び水の存在下、窒化アル
ミニウム粉末を燐酸化合物で処理し、流動性改良剤を混
合することを特徴とする窒化アルミニウム粉末の製造方
法に関する。That is, the present invention comprises a flow improver, and
Aluminum nitride powder treated with a phosphate compound
And the phosphoric acid compound is P with respect to the aluminum nitride powder.
2O 50.1 to 10% by weight
Excellent fluidity and water resistance, dissolution of ionic components
Low aluminum nitride powder and aluminum nitride in the presence of water
Minium powder is treated with a phosphate compound and mixed with a fluidity improver.
For producing aluminum nitride powder characterized by combining
About the law.
【００１０】[0010]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明で用いる窒化アルミニウム粉末は、製法による差
異は認められず、通常用いられる窒化アルミニウム粉末
が使用できる。例えば、有機アルミニウム化合物とアン
モニアを反応さた後、加熱する気相反応法、アルミナと
炭素の混合物を窒素中で加熱するアルミナ還元法、アル
ミニウムと窒素で反応させる直接窒化法等で製造した窒
化アルミニウム粉末がいずれも好適に使用可能である。
その中でも樹脂との馴染みが良く、多量に樹脂に充填す
ることが可能である気相反応法により得られる窒化アル
ミニウム粉末を使用するのが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The aluminum nitride powder used in the present invention does not differ depending on the production method, and a commonly used aluminum nitride powder can be used. For example, aluminum nitride manufactured by a gas phase reaction method in which an organic aluminum compound is reacted with ammonia and then heating, an alumina reduction method in which a mixture of alumina and carbon is heated in nitrogen, and a direct nitriding method in which aluminum and nitrogen are reacted with aluminum. Any powder can be suitably used.
Among them, it is preferable to use an aluminum nitride powder obtained by a gas phase reaction method, which has good compatibility with the resin and can be filled in a large amount in the resin.
【００１１】本発明でいう燐酸化合物で処理された窒化
アルミニウム粉末とは、窒化アルミニウム粉末表面に燐
酸化合物を含有する窒化アルミニウム粉末であって、窒
化アルミニウム粉末表面のアルミニウムの少なくとも一
部が燐酸アルミニウム結合（Ａｌ−Ｏ−Ｐ）を形成して
いる窒化アルミニウム粉末をいい、その周辺の結合状態
が特定されるものではない。おそらくは、この燐酸アル
ミニウムの層が耐水性の層であると本発明者らは考えて
おり、Ａｌ−Ｏ−Ｐ結合の多少により、高温耐水性、長
時間耐水性等の性能を付与できることを実験的に確認し
ている。The aluminum nitride powder treated with a phosphate compound in the present invention is an aluminum nitride powder containing a phosphate compound on the surface of the aluminum nitride powder, wherein at least a part of the aluminum on the surface of the aluminum nitride powder is bonded to aluminum phosphate. It refers to the aluminum nitride powder forming (Al-OP), and the surrounding bonding state is not specified. Probably, the present inventors consider that this aluminum phosphate layer is a water-resistant layer, and have conducted experiments to show that some degree of Al-OP bonding can impart properties such as high-temperature water resistance and long-time water resistance. I'm sure.
【００１２】また、本発明では窒化アルミニウム粉末の
表面に存在する燐酸化合物（燐酸アルミニウム）のＰ２
Ｏ５換算で含有量を特定することによって、窒化アルミ
ニウムに優れた耐水性を付与することができる。Further, according to the present invention, P 2 of a phosphoric acid compound (aluminum phosphate) existing on the surface of aluminum nitride powder is used.
By specifying the content in terms of O 5 , excellent water resistance can be imparted to aluminum nitride.
【００１３】この耐水性窒化アルミニウム粉末は、燐酸
化合物をＰ２Ｏ５換算で０．１〜１０重量％の範囲で含
有する必要があり、好ましくは、０．３〜８重量％、更
に好ましくは、０．５〜６重量の範囲が好適である。耐
水性窒化アルミニウム粉末のＰ２Ｏ５含有量が０．１重
量％未満では、所望の耐水性を得ることができず、ま
た、１０重量％を超えると、所望の耐水性と流動性は得
られるが、窒化アルミニウムの酸素含有量が高くなり窒
化アルミニウム粉末本来の特性である熱伝導性を損な
う。また、未反応の燐酸化合物が多くなるため、溶出性
の燐酸化合物が増加し、溶出性のイオン性成分の増加に
つながるので好ましくない。This water-resistant aluminum nitride powder must contain a phosphoric acid compound in the range of 0.1 to 10% by weight in terms of P 2 O 5 , preferably 0.3 to 8% by weight, and more preferably 0.3 to 8% by weight. , 0.5 to 6% by weight is preferred. If the P 2 O 5 content of the water-resistant aluminum nitride powder is less than 0.1% by weight, desired water resistance cannot be obtained, and if it exceeds 10% by weight, desired water resistance and fluidity cannot be obtained. However, the oxygen content of aluminum nitride is increased, and the thermal conductivity, which is an inherent characteristic of aluminum nitride powder, is impaired. Further, since the unreacted phosphoric acid compound increases, the dissolvable phosphoric acid compound increases, which leads to an increase in the dissolvable ionic component, which is not preferable.
【００１４】本発明の窒化アルミニウム粉末の燐酸化合
物での処理とは、燐酸化合物と窒化アルミニウム粉末を
接触させる操作をいい、例えば窒化アルミニウム粉末を
燐酸化合物溶液に分散させることや窒化アルミニウム粉
末を燐酸化合物溶液に練り込みペースト状にすること等
が挙げられる。燐酸化合物と窒化アルミニウムが接触す
る操作であれば、どのような方法でもよい。The treatment of the aluminum nitride powder with a phosphate compound according to the present invention refers to an operation of bringing the phosphate compound into contact with the aluminum nitride powder. For example, dispersing the aluminum nitride powder in a phosphate compound solution or treating the aluminum nitride powder with a phosphate compound And kneading it into a solution to form a paste. Any method may be used as long as the phosphate compound and aluminum nitride are in contact with each other.
【００１５】本発明でいう燐酸化合物とは、窒化アルミ
ニウム粉末表面のアルミニウムと反応して燐酸アルミニ
ウム結合（Ａｌ−Ｏ−Ｐ結合）を形成し、最終的には窒
化アルミニウム粉末を燐酸アルミニウム層で被覆する能
力を有する燐酸化合物を意味し、例えば、オルト燐酸、
メタ燐酸、ピロ燐酸、ポリ燐酸、ホスホン酸等の無機燐
酸化合物やメチルアシッドホスフェート、エチルアシッ
ドホスフェート、ブチルアシッドホスフェート、２−エ
チルヘキシルアシッドホスフェート、ラウリルアッシド
ホスフェート、パルミチルアッシドホスフェート、ステ
アリルアシッドホスフェート、オレイルアシッドホスフ
ェート、フェニルアシッドホスフェート、ノニルフェニ
ルアシッドホスフェート等の酸性燐酸エステル類、ジ−
２−エチルヘキシルピロホスフェート等のピロ燐酸又は
ポリ燐酸のモノ若しくはジアルキル、アルケニル又はア
リールエステル類、メチレンホスホン酸、アミノメチレ
ンホスホン酸等のホスホン酸類及びそのエステル類等の
有機燐酸化合物等がその例として挙げられる。また、二
種類以上の燐酸化合物の混合物でもかまわない。In the present invention, the phosphoric acid compound reacts with aluminum on the surface of the aluminum nitride powder to form an aluminum phosphate bond (Al-OP bond), and finally coats the aluminum nitride powder with an aluminum phosphate layer. Means a phosphoric acid compound capable of, for example, orthophosphoric acid,
Inorganic phosphate compounds such as metaphosphoric acid, pyrophosphoric acid, polyphosphoric acid and phosphonic acid, and methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, 2-ethylhexyl acid phosphate, lauryl acid phosphate, palmityl acid phosphate, stearyl acid phosphate, Acid phosphates such as oleyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate,
Mono- or dialkyl, alkenyl or aryl esters of pyrophosphoric acid or polyphosphoric acid such as 2-ethylhexyl pyrophosphate, phosphonic acids such as methylenephosphonic acid and aminomethylenephosphonic acid, and organic phosphoric acid compounds such as esters thereof are mentioned as examples. Can be Further, a mixture of two or more phosphoric acid compounds may be used.
【００１６】本発明では燐酸化合物を溶液として用い
る。その際、上記の燐酸化合物を水または水と有機溶剤
に溶解したものを用いる。用いる水としては、純水でも
市水でもよい。また、有機溶剤としては、燐酸化合物が
溶解するものなら何でもよいが、水の存在が必要なこと
から水溶性であることが好ましい。例えば、メタノー
ル、エタノール、イソプロパノール、ブタノール、テト
ラヒドロキシフラン（ＴＨＦ）等が挙げられる。このよ
うな水溶性の有機溶剤に溶けない燐酸化合物の場合、水
溶性の有機溶剤と共にヘキサン、ヘプタン、ベンゼン、
トルエン等の非水溶性の有機溶剤を併用してもよい。こ
こで用いる燐酸化合物の濃度は、特に限定されるもので
はないが、濃度が０．０１重量％以下では、所望の耐水
性が得られないので好ましくない。In the present invention, a phosphate compound is used as a solution. At that time, the above-mentioned phosphoric acid compound dissolved in water or water and an organic solvent is used. Pure water or city water may be used as the water. Any organic solvent may be used as long as the phosphoric acid compound can be dissolved, but it is preferably water-soluble because the presence of water is required. For example, methanol, ethanol, isopropanol, butanol, tetrahydroxyfuran (THF) and the like can be mentioned. In the case of a phosphoric acid compound that does not dissolve in such a water-soluble organic solvent, hexane, heptane, benzene,
A water-insoluble organic solvent such as toluene may be used in combination. The concentration of the phosphoric acid compound used here is not particularly limited, but a concentration of 0.01% by weight or less is not preferable because desired water resistance cannot be obtained.
【００１７】窒化アルミニウム粉末に対する燐酸化合物
の使用量は、窒化アルミニウム粉末１００重量部に対し
て０．０３〜２００重量部の範囲が好ましく、更に好ま
しくは０．３〜１００重量部、最も好ましくは０．３〜
６０重量部が好適である。窒化アルミニウム粉末１００
重量部に対して０．０３重量部未満では、所望の耐水性
を得ることができず、また、２００重量部を超えると、
所望の耐水性及び流動性は得られるが、窒化アルミニウ
ムの酸素含有量が高くなり窒化アルミニウム本来の特性
である熱伝導性を損なうので好ましくない。また、未反
応の燐酸化合物が多くなるため、溶出性の燐酸化合物が
増加し、溶出性のイオン性成分の増加につながるので好
ましくない。The amount of the phosphoric acid compound used in the aluminum nitride powder is preferably in the range of 0.03 to 200 parts by weight, more preferably 0.3 to 100 parts by weight, most preferably 0 to 100 parts by weight based on 100 parts by weight of the aluminum nitride powder. .3 ~
60 parts by weight are preferred. Aluminum nitride powder 100
If it is less than 0.03 parts by weight, desired water resistance cannot be obtained, and if it exceeds 200 parts by weight,
Although desired water resistance and fluidity can be obtained, it is not preferable because the oxygen content of aluminum nitride is increased and thermal conductivity, which is an inherent property of aluminum nitride, is impaired. Further, since the unreacted phosphoric acid compound increases, the dissolvable phosphoric acid compound increases, which leads to an increase in the dissolvable ionic component, which is not preferable.
【００１８】窒化アルミニウム粉末を燐酸化合物で処理
する際に水が存在することが、本発明では重要なポイン
トとなる。というのは、水が存在することにより窒化ア
ルミニウム粉末の表面を強制的に加水分解し、燐酸化合
物と反応する活性点である水酸化アルミニウムを発生さ
せる。この活性点の増加により燐酸アルミニウム結合
（燐酸アルミニウムの層）の形成を促進するので、高い
耐水性が得られる。このことについては、発明者らは実
験的に確認している。水の使用量は窒化アルミニウム粉
末１００重量部に対して１重量部以上必要である。窒化
アルミニウム粉末１００重量部に対して１重量部未満で
は活性点が増加しないため耐水性の層の形成を促進され
ず、高い耐水性は得られないので好ましくない。また、
耐水性の層の形成は、非常に速いので水による加水分解
が進行し、窒化アルミニウム粉末本来の特性を損なうこ
とはない。The important point of the present invention is that water is present when the aluminum nitride powder is treated with the phosphate compound. That is, the presence of water forcibly hydrolyzes the surface of the aluminum nitride powder to generate aluminum hydroxide, which is an active site that reacts with the phosphate compound. The increase in the number of active sites promotes the formation of an aluminum phosphate bond (a layer of aluminum phosphate), so that high water resistance can be obtained. This has been experimentally confirmed by the inventors. The amount of water used must be at least 1 part by weight based on 100 parts by weight of aluminum nitride powder. If the amount is less than 1 part by weight with respect to 100 parts by weight of the aluminum nitride powder, the active sites do not increase, so that formation of a water-resistant layer is not promoted, and high water resistance cannot be obtained. Also,
Since the formation of the water-resistant layer is very fast, the hydrolysis with water proceeds, and the inherent properties of the aluminum nitride powder are not impaired.
【００１９】窒化アルミニウム粉末を燐酸化合物で処理
する温度は、燐酸化合物や水の使用量等の条件により一
概にはいえないが、０〜１００℃の範囲が好ましく、更
に好ましくは１８〜５０℃が好適である。処理する温度
が０℃未満では、窒化アルミニウム表面が加水分解しに
くいので、燐酸化合物との反応する活性点が増加しない
ため、燐酸化合物との反応が進行しないので、所望の耐
水性が得らない、また、処理する温度が１００℃を超え
ると、耐水性は得られるが、窒化アルミニウム粉末と燐
酸化合物の反応が進行し過ぎて窒化アルミニウム粉末本
来の特性を損なってしまうので好ましくない。The temperature at which the aluminum nitride powder is treated with the phosphoric acid compound cannot be unconditionally determined depending on conditions such as the amount of the phosphoric acid compound and water, but is preferably in the range of 0 to 100 ° C., more preferably 18 to 50 ° C. It is suitable. If the treatment temperature is lower than 0 ° C., the surface of the aluminum nitride is hardly hydrolyzed, so that the number of active sites that react with the phosphoric acid compound does not increase, and the reaction with the phosphoric acid compound does not proceed, so that desired water resistance cannot be obtained. If the treatment temperature exceeds 100 ° C., water resistance is obtained, but the reaction between the aluminum nitride powder and the phosphoric acid compound proceeds excessively, and the inherent properties of the aluminum nitride powder are undesirably impaired.
【００２０】窒化アルミニウム粉末と燐酸化合物を処理
する時間は、燐酸化合物の濃度、使用量、温度等により
一概にはいえないが１〜１２０分が好ましく、更に好ま
しくは、５〜６０分が好適である。The time for treating the aluminum nitride powder and the phosphoric acid compound cannot be determined unconditionally depending on the concentration, amount, temperature, etc. of the phosphoric acid compound, but is preferably from 1 to 120 minutes, more preferably from 5 to 60 minutes. is there.
【００２１】上記の燐酸化合物の処理に加えて、更に流
動性改良剤の混合を行うことで、窒化アルミニウム粉末
への更に優れた耐水性の付与イオン性成分の溶出の
抑制優れた流動性の付与という目的を達成することが
できる。著しい性能向上の理由としては、燐酸アルミニ
ウムの層を有する窒化アルミニウム粉末の表面に流動性
改良剤の粒子が存在するためと推測している。おそら
く、燐酸化合物を有する窒化アルミニウム粉末表面に流
動性改良剤の粒子が存在することより、未反応の燐酸化
合物の溶出が抑制されることによって、燐酸化合物の溶
出による耐水性の低下が抑えられ、結果として、耐水性
の向上とイオン性成分の溶出の抑制をもたらすと考えて
よい。In addition to the above-mentioned treatment of the phosphoric acid compound, by further mixing a fluidity improver, more excellent water resistance can be imparted to the aluminum nitride powder. The purpose can be achieved. It is speculated that the reason for the remarkable improvement in performance is that particles of the fluidity improver are present on the surface of the aluminum nitride powder having the aluminum phosphate layer. Probably, due to the presence of particles of the fluidity improver on the surface of the aluminum nitride powder having the phosphate compound, the elution of the unreacted phosphate compound is suppressed, whereby the decrease in water resistance due to the elution of the phosphate compound is suppressed, As a result, it may be considered that the water resistance is improved and the elution of the ionic component is suppressed.
【００２２】本発明でいう流動性改質剤としてはシリ
カ、アルミナ、チタニア、窒化ほう素及び表面に親油性
基を有する無機粉末等が挙げられる。また、２種類以上
の流動性改質剤の混合物でもかまわない。これらの流動
性改質剤の粒径は１μｍ以下が好ましい。Examples of the fluidity modifier referred to in the present invention include silica, alumina, titania, boron nitride, and inorganic powder having a lipophilic group on the surface. Also, a mixture of two or more fluidity modifiers may be used. The particle size of these fluidity modifiers is preferably 1 μm or less.
【００２３】本発明の表面に親油性基を有する無機粉末
とは、無機粉末の表面を樹脂、シリコンオイル、シリコ
ーンやフッ素化合物等で被覆して、無機粉末の表面を親
油性基で覆われた無機粉末のことを意味する。例えば、
表面に親油性基を有するシリカ（以下、撥水性シリカと
記す）等が挙げられる。In the present invention, the term "inorganic powder having a lipophilic group on the surface" means that the surface of the inorganic powder is covered with a resin, silicone oil, silicone or a fluorine compound, and the surface of the inorganic powder is covered with a lipophilic group. Means inorganic powder. For example,
Silica having a lipophilic group on its surface (hereinafter referred to as water-repellent silica) and the like can be mentioned.
【００２４】特に、流動性改質剤として表面に親油性基
を有する無機粉末を用いた場合、窒化アルミニウムの耐
水性、流動性が著しく改善され、更にイオン性成分の溶
出を抑制する効果も大きい。その上、窒化アルミニウム
と表面に親油性基を有する無機粉末が混合することで、
樹脂との馴染みも他のものより向上するので、樹脂への
分散性も著しく向上する。In particular, when an inorganic powder having a lipophilic group on the surface is used as a fluidity modifier, the water resistance and fluidity of aluminum nitride are remarkably improved, and the effect of suppressing elution of ionic components is also great. . In addition, by mixing aluminum nitride and inorganic powder having a lipophilic group on the surface,
Since the familiarity with the resin is improved as compared with the others, the dispersibility in the resin is also significantly improved.
【００２５】流動性改良剤として表面に親油性基を有す
る無機粉末を用いる場合、混合の際に分散剤として有機
溶剤を用いると、他の方法と比較すると耐水性の向上及
びイオン性成分の溶出抑制の効果が非常に大きい。分散
剤を用いて表面に親油性基を有する無機粉末を混合する
方法が他の方法に類を見ない程に耐水性の向上及びイオ
ン性成分の溶出抑制の効果をもたらす理由としては、お
そらく有機溶剤により無機粉末表面の親油性の被覆剤が
溶出し、この親油性の被覆剤が窒化アルミニウム表面を
覆うため窒化アルミニウム表面をすきまなく被覆するこ
ととなり、流動性改良剤の粒子が窒化アルミニウム表面
に存在するだけのものよりも耐水性の向上とイオン性成
分の溶出の効果が大きくなる、と推測している。無機粉
末表面にどのような親油性の被覆剤を含有するものでも
同様の効果が得られるが、特に、無機粉末の表面をシリ
コンオイルで被覆した無機粉末が有用である。ここで用
いる分散剤としての有機溶媒は水溶性のものならば、何
でもよく、例えばメタノール、エタノール、イソプロパ
ノール、ブタノール、テトラヒドロキシフラン（ＴＨ
Ｆ）等が挙げられる。また、ヘプタン、ヘキサン、ベン
ゼン、トルエン、クロロホルム等の非水溶性の有機溶剤
を併用してもよい。When an inorganic powder having a lipophilic group on its surface is used as a fluidity improver, the use of an organic solvent as a dispersant during mixing improves water resistance and elutes ionic components as compared with other methods. The effect of suppression is very large. The reason why the method of mixing the inorganic powder having a lipophilic group on the surface with the use of a dispersant brings about the effect of improving the water resistance and suppressing the elution of the ionic component as unparalleled as other methods is probably organic. The lipophilic coating agent on the surface of the inorganic powder is eluted by the solvent, and this lipophilic coating agent covers the aluminum nitride surface, so that the aluminum nitride surface is covered without gaps, and particles of the fluidity improver are coated on the aluminum nitride surface. It is presumed that the effects of improving water resistance and eluting ionic components are greater than those that only exist. The same effect can be obtained by containing any lipophilic coating agent on the surface of the inorganic powder. In particular, an inorganic powder in which the surface of the inorganic powder is coated with silicone oil is useful. The organic solvent as a dispersant used herein may be any organic solvent as long as it is water-soluble, such as methanol, ethanol, isopropanol, butanol, tetrahydroxyfuran (TH
F) and the like. Further, a water-insoluble organic solvent such as heptane, hexane, benzene, toluene and chloroform may be used in combination.
【００２６】分散剤を用いた表面に親油性基を有する無
機粉末の混合は、燐酸化合物処理の後でも燐酸化合物処
理の際のいつでもよく、均一に混合することができれば
いつ行ってもよい。燐酸化合物で処理の後に混合する方
法としては、窒化アルミニウム粉末又は表面に親油性基
を有する無機粉末をスラリーとして、ミキサーやボール
ミル等を用いて均一に混合する方法等がある。The mixing of the inorganic powder having a lipophilic group on the surface using the dispersant may be carried out at any time after the treatment with the phosphate compound or at the time of the treatment with the phosphate compound, and may be carried out at any time as long as uniform mixing is possible. As a method of mixing after the treatment with the phosphate compound, there is a method of uniformly mixing the aluminum nitride powder or the inorganic powder having a lipophilic group on the surface using a mixer or a ball mill.
【００２７】燐酸化合物で処理の際に混合する方法とし
ては、予め分散剤で表面に親油性基を有する無機粉末を
スラリー又はペースト状にして混合する方法と分散剤が
含まれている燐酸化合物溶液中の表面に親油性基を有す
る無機粉末をそのまま添加し、混合する方法等がある。
前者の方が分散剤の使用量が少量でよく、低コストで製
造できる。特に、オルト燐酸等の無機燐酸の水溶液で窒
化アルミニウム粉末を処理し、流動性改良剤として表面
に親油性基を有する無機粉末を用いる場合、均一に混合
するために分散剤として有機溶媒を用いて流動性改良剤
をスラリー又はペースト状にする必要がある。As a method of mixing with the phosphate compound at the time of treatment, a method of mixing an inorganic powder having a lipophilic group on the surface with a dispersant in advance in a slurry or paste form and a method of mixing a phosphate compound solution containing the dispersant There is a method in which an inorganic powder having a lipophilic group is directly added to the inner surface and mixed.
In the former case, the amount of the dispersant used may be small, and it can be produced at low cost. In particular, when treating aluminum nitride powder with an aqueous solution of inorganic phosphoric acid such as orthophosphoric acid and using an inorganic powder having a lipophilic group on the surface as a fluidity improver, use an organic solvent as a dispersant to uniformly mix. The flow improver must be in the form of a slurry or paste.
【００２８】分散剤を使用しない場合、流動性改良剤の
混合は、燐酸化合物処理の後でも、燐酸化合物処理の際
に行ってもよく、流動性改良剤が均一に窒化アルミニウ
ム粉末と混合できればよい。燐酸化合物処理の後、流動
性改良剤を混合する方法としては、ヘンシェルミキサ
ー、Ｖブレンダー等を用いて、粉体同士を混合する方法
とボールミルを用いて、粉砕混合する方法がある。後者
の方法の方が性能の向上の効果が大きい。When the dispersant is not used, the mixing of the fluidity improver may be performed after the phosphate compound treatment or during the phosphate compound treatment, provided that the fluidity improver can be uniformly mixed with the aluminum nitride powder. . As a method of mixing the fluidity improver after the phosphate compound treatment, there are a method of mixing powders using a Henschel mixer, a V blender, and the like, and a method of pulverizing and mixing using a ball mill. The latter method has a greater effect of improving performance.
【００２９】燐酸化合物処理の際に流動性改良剤を混合
する方法としては、窒化アルミニウム粉末を燐酸化合物
溶液に分散させてスラリーに流動性改良剤を分散させる
方法、窒化アルミニウム粉末を燐酸化合物溶液に練り込
みペースト状に流動性改良剤を練り込む方法や、前もっ
て流動性改良剤を燐酸化合物溶液に分散させた後、窒化
アルミニウム粉末を燐酸化合物で処理する方法等があ
る。また、流動性改良剤を溶媒でスラリー又はペースト
状にしてから混合してもかまわない。As a method of mixing the fluidity improver during the treatment with the phosphate compound, a method in which aluminum nitride powder is dispersed in a phosphate compound solution to disperse the fluidity improver in a slurry, and a method in which the aluminum nitride powder is dispersed in the phosphate compound solution There are a method of kneading the fluidity improver into a kneading paste, a method of dispersing the fluidity improver in a phosphate compound solution in advance, and then treating the aluminum nitride powder with a phosphate compound. Also, the fluidity improver may be mixed in a slurry or paste form with a solvent.
【００３０】燐酸化合物での処理及び流動性改良剤の混
合を行った窒化アルミニウムのスラリーを濾過し、過剰
の燐酸化合物を取り除くため、水または有機溶媒で洗浄
を行った後、乾燥、粉砕する。この濾過〜乾燥を繰り返
すことにより、より高純度の流動性及び耐水性に優れ、
イオン性成分の溶出性の低い窒化アルミニウム粉末が得
られる。また、燐酸化合物で処理及び流動性改良剤の混
合を行った窒化アルミニウム粉末のスラリーをそのまま
スプレードライを用いて乾燥する方法、また上記したよ
うに濾過してそのケーキを乾燥する方法等いずれの方法
でも構わない。窒化アルミニウムスラリーの濾過は、ヌ
ッチェ、遠心濾過機等を使用する。また、濾過を行わず
そのまま乾燥を行ってもよい。The aluminum nitride slurry which has been treated with a phosphate compound and mixed with a fluidity improver is filtered, washed with water or an organic solvent, dried and pulverized to remove excess phosphate compound. By repeating this filtration to drying, the fluidity and water resistance of higher purity are excellent,
An aluminum nitride powder having a low ionic component elution property is obtained. Also, any method such as a method of drying the slurry of the aluminum nitride powder which has been treated with the phosphate compound and mixed with the fluidity improver using spray drying as it is, or a method of drying the cake by filtration as described above. But it doesn't matter. For filtration of the aluminum nitride slurry, a Nutsche, centrifugal filter or the like is used. Further, the drying may be performed without filtering.
【００３１】所定量の燐酸化合物及び流動性改良剤を用
いて窒化アルミニウム粉末をペースト状にして処理を行
った場合は、そのまま乾燥し、粉砕することで所望の流
動性及び耐水性に優れ、イオン性成分の溶出性の低い窒
化アルミニウム粉末を得ることができる。この方法によ
り流動性及び耐水性に優れ、イオン性成分の溶出性の低
い窒化アルミニウム粉末を低コストで多量に製造するこ
とができる。When aluminum nitride powder is processed into a paste using a predetermined amount of a phosphoric acid compound and a fluidity improver, the powder is dried as it is and then pulverized to obtain desired fluidity and water resistance. It is possible to obtain an aluminum nitride powder having a low dissolution property of a conductive component. According to this method, a large amount of aluminum nitride powder having excellent fluidity and water resistance and low elution of ionic components can be produced at low cost.
【００３２】乾燥方法としては、濾過したケーキ、スラ
リーやペーストを８０〜３００℃で３〜２４時間乾燥さ
せる。用いる乾燥機には、熱風乾燥機、蒸気乾燥機等を
用いるのが好ましい。As a drying method, the filtered cake, slurry or paste is dried at 80 to 300 ° C. for 3 to 24 hours. It is preferable to use a hot air dryer, a steam dryer, or the like as the dryer to be used.
【００３３】粉砕には、ジェットミル、サンプルミル、
ボールミル等を用いる。また、ここでいう粉砕は、二次
粒子を一次粒子にすることであり、被覆表面を破壊する
ものではない。For grinding, a jet mill, a sample mill,
Use a ball mill or the like. Further, the pulverization referred to here is to convert the secondary particles into primary particles, and does not destroy the coating surface.
【００３４】以上のような方法で得た流動性及び耐水性
に優れ、イオン性成分の溶出性の低い窒化アルミニウム
粉末に対し、以下の方法で更にイオン性成分の溶出を抑
制することができる。つまり、イオン性成分の溶出を抑
制する方法としては、１５０〜６００℃で加熱処理する
ことにより燐酸アルミニウム結合（Ａｌ−Ｏ−Ｐ）の生
成を促進させる方法や洗浄により溶出性のイオン性成分
の除去をする方法等がある。また、加熱処理と洗浄を組
み合わせることにより効果的にイオン性成分の溶出を抑
制することができる。これらのイオン性成分の溶出を抑
制する方法を用いることにより、更に高純度の流動性及
び耐水性に優れ、イオン性成分の溶出性の低い窒化アル
ミニウム粉末が得られる。The elution of ionic components can be further suppressed by the following method with respect to the aluminum nitride powder having excellent fluidity and water resistance and low elution of ionic components obtained by the above method. That is, as a method of suppressing the elution of the ionic component, a method of promoting the formation of an aluminum phosphate bond (Al-OP) by heat treatment at 150 to 600 ° C. or a method of suppressing the elution of the ionic component by washing is used. There is a method of removing. Further, the elution of the ionic component can be effectively suppressed by combining the heat treatment and the washing. By using the method of suppressing the elution of these ionic components, an aluminum nitride powder having higher purity and excellent fluidity and water resistance and lower elution of the ionic components can be obtained.
【００３５】[0035]
【実施例】以下、本発明を実施例をもって説明する。％
及び部は特記しないかぎり重量基準で表す。 実施例１ ２．４％オルト燐酸水溶液５６．８部（オルト燐酸１．
４部、水５５．４部）に予め、窒化アルミニウム粉末に
対して２％の撥水性シリカをメタノールでスラリーにし
て加え、オルト燐酸水溶液中に分散させた。次に前記の
オルト燐酸水溶液に窒化アルミニウム粉末（平均粒径１
μｍ）１００部を加え、５Ｌのニーダーで練り込みペー
スト状とし、３０℃で３０分間処理を行った。この混合
物を１２０℃、８時間乾燥し、乾燥後、ジェットミルで
粉砕し、窒化アルミニウム粉末を得た。The present invention will be described below with reference to examples. %
Parts and parts are expressed on a weight basis unless otherwise specified. Example 1 56.8 parts of a 2.4% aqueous solution of orthophosphoric acid (orthophosphoric acid 1.
(4 parts, water 55.4 parts), 2% of water-repellent silica with respect to the aluminum nitride powder was previously slurried with methanol and dispersed in an orthophosphoric acid aqueous solution. Next, aluminum nitride powder (average particle size: 1) was added to the above-mentioned orthophosphoric acid solution.
μm), and kneaded with a 5 L kneader to form a paste, which was then treated at 30 ° C. for 30 minutes. This mixture was dried at 120 ° C. for 8 hours, and after drying, pulverized with a jet mill to obtain an aluminum nitride powder.
【００３６】得られた窒化アルミニウム粉末の評価試験
は下記の方法で行った。 ・窒化アルミニウム粉末の表面の燐含有量 窒化アルミニウム粉末１．５ｇを水酸化ナトリウム水溶
液中で、加熱溶解し、中和後、比色分析を行い、耐水性
窒化アルミニウム粉末表面の燐含有量を測定した。 ・窒化アルミニウム粉末の耐水性試験 純水１００ｇを１００℃まで加熱し、１００℃に達した
純水中に窒化アルミニウム粉末１ｇを分散させ、分散後
の分散液のｐＨ変化を経時的に測定した。 ・電気伝導率の測定 耐水性試験を行った分散液を濾過し、その濾液の電気伝
導率を測定することで、溶出イオン性成分の評価を行っ
た。 ・また、安息角を測定することで、流動性の評価を行っ
た。 ・窒化アルミニウム粉末の溶出性テスト テフロンコーティングをしたステンレス製容器に純水１
００ｇと窒化アルミニウム粉末１２．５ｇを入れて容器
を密閉した。これを１２０℃で２４時間加熱し、冷却後
濾過し、その濾液のｐＨ及び電気伝導率を測定した。こ
れらの評価結果を表１に示す。The evaluation test of the obtained aluminum nitride powder was performed by the following method.・ Phosphorus content on the surface of aluminum nitride powder 1.5 g of aluminum nitride powder is heated and dissolved in an aqueous sodium hydroxide solution, neutralized, colorimetrically analyzed, and the phosphorus content on the surface of the water-resistant aluminum nitride powder is measured. did. Water Resistance Test of Aluminum Nitride Powder 100 g of pure water was heated to 100 ° C., 1 g of aluminum nitride powder was dispersed in the pure water that reached 100 ° C., and the pH change of the dispersion after dispersion was measured with time. -Measurement of electric conductivity The dispersion subjected to the water resistance test was filtered, and the elution ionic component was evaluated by measuring the electric conductivity of the filtrate.・ Fluidity was evaluated by measuring the angle of repose.・ Elutability test of aluminum nitride powder Pure water 1 in a Teflon-coated stainless steel container
00g and 12.5g of aluminum nitride powder were charged and the container was closed. This was heated at 120 ° C. for 24 hours, cooled and filtered, and the pH and electric conductivity of the filtrate were measured. Table 1 shows the results of these evaluations.
【００３７】実施例２〜３ 撥水性シリカの添加量を５％、１０％に変更した以外は
実施例１と同様の方法で窒化アルミニウム粉末を得た。
得られた窒化アルミニウム粉末の燐含有量、耐水性、溶
出イオン性成分及び流動性の評価を実施例１と同様に行
い、その結果を表１に示す。Examples 2-3 An aluminum nitride powder was obtained in the same manner as in Example 1, except that the amount of water-repellent silica was changed to 5% and 10%.
The phosphorus content, water resistance, eluting ionic component and fluidity of the obtained aluminum nitride powder were evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００３８】実施例４ ２．４％オルト燐酸水溶液を６．８％オルト燐酸水溶液
６０．５部（オルト燐酸４．１部、水５６．４部）に変
更した以外は、実施例１と同様の方法で窒化アルミニウ
ム粉末を得た。得られた窒化アルミニウム粉末の燐含有
量、耐水性、溶出イオン性成分及び流動性の評価を実施
例１と同様に行い、その結果を表１に示す。Example 4 Same as Example 1 except that the 2.4% aqueous orthophosphoric acid solution was changed to 60.5 parts of a 6.8% aqueous orthophosphoric acid solution (4.1 parts of orthophosphoric acid, 56.4 parts of water). In this manner, an aluminum nitride powder was obtained. The phosphorus content, water resistance, eluting ionic component and fluidity of the obtained aluminum nitride powder were evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００３９】実施例５ ２．４％オルト燐酸水溶液を１５．８％オルト燐酸水溶
液６９．７部（オルト燐酸１１部、水５８．７部）に変
更した以外は、実施例１と同様の方法で窒化アルミニウ
ム粉末のを得た。得られた窒化アルミニウム粉末の燐含
有量、耐水性、溶出イオン性成分及び流動性の評価を実
施例１と同様に行い、その結果を表１に示す。Example 5 A method similar to that of Example 1 except that the 2.4% aqueous orthophosphoric acid solution was changed to 69.7 parts of an aqueous 15.8% orthophosphoric acid solution (11 parts of orthophosphoric acid and 58.7 parts of water). Thus, an aluminum nitride powder was obtained. The phosphorus content, water resistance, eluting ionic component and fluidity of the obtained aluminum nitride powder were evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００４０】実施例６〜７ 流動性改良剤をアルミナ、窒化ほう素に変更した以外
は、実施例１と同様の方法で窒化アルミニウム粉末を得
た。得られた窒化アルミニウム粉末の燐含有量、耐水
性、溶出イオン性成分及び流動性の評価を実施例１と同
様に行い、その結果を表１に示す。Examples 6 and 7 Aluminum nitride powder was obtained in the same manner as in Example 1 except that the fluidity improver was changed to alumina and boron nitride. The phosphorus content, water resistance, eluting ionic component and fluidity of the obtained aluminum nitride powder were evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００４１】実施例８ 容量５Ｌのガラス製容器に１３％ピロ燐酸水溶液２３０
部（ピロ燐酸３０部、水２００部）を入れ、このピロ燐
酸水溶液に窒化アルミニウム粉末（平均粒径１μｍ）１
００部を加えて水溶液中に分散させ、処理温度８０℃で
１５分間処理を行い窒化アルミニウム粉末のスラリーを
得た。更に、窒化アルミニウム粉末に対して２％の撥水
性シリカをメタノールでスラリーにし、窒化アルミニウ
ム粉末のスラリーに分散させた。このスラリーを濾過
し、過剰のピロ燐酸水溶液を取り除くため２００部の水
で洗浄を行った後、１２０℃、３時間、乾燥し、乾燥
後、ジェットミルで粉砕し窒化アルミニウム粉末を得
た。得られた窒化アルミニウム粉末の燐含有量、耐水
性、溶出イオン性成分及び流動性の評価を実施例１と同
様に行い、その結果を表１に示す。Example 8 A 13% aqueous solution of pyrophosphoric acid was placed in a 5 L glass container.
Parts (30 parts of pyrophosphoric acid, 200 parts of water) were added to the aqueous solution of pyrophosphoric acid, and aluminum nitride powder (average particle size: 1 μm)
After adding 00 parts, the mixture was dispersed in an aqueous solution and treated at a treatment temperature of 80 ° C. for 15 minutes to obtain a slurry of aluminum nitride powder. Further, 2% of water-repellent silica with respect to the aluminum nitride powder was slurried with methanol and dispersed in the aluminum nitride powder slurry. The slurry was filtered, washed with 200 parts of water to remove excess pyrophosphoric acid aqueous solution, dried at 120 ° C. for 3 hours, dried, and pulverized with a jet mill to obtain aluminum nitride powder. The phosphorus content, water resistance, eluting ionic component and fluidity of the obtained aluminum nitride powder were evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００４２】実施例９ 容量５Ｌのガラス製容器にイソプロパノール／純水＝９
／１（重量比）の割合のものを２５０部とエチルアシッ
ドホスフェート３０部を混合し、この混合液に窒化アル
ミニウム粉末（平均粒径１μｍ）１００部を加え分散さ
せ、処理温度５０℃で３０分間処理を行った（窒化アル
ミニウム粉末／エチルアシッドホスフェート／水＝１０
０部／３０部／２５部）。更に、窒化アルミニウム粉末
に対して２％の撥水性シリカを分散させた。このスラリ
ーを濾過し、過剰のエチルアシッドホスフェートを取り
除くため、１０００部のイソプロパノールで洗浄した。
これを８０℃、５時間乾燥した後、ジェットミルで粉砕
し、窒化アルミニウム粉末を得た。得られた窒化アルミ
ニウム粉末の燐含有量、耐水性、溶出イオン性成分及び
流動性の評価を実施例１と同様に行い、その結果を表１
に示す。EXAMPLE 9 Isopropanol / pure water = 9 was placed in a glass container having a capacity of 5 L.
/ 1 (weight ratio) of 250 parts and 30 parts of ethyl acid phosphate were mixed, and 100 parts of aluminum nitride powder (average particle size: 1 µm) was added and dispersed in the mixture, and the mixture was treated at a processing temperature of 50 ° C for 30 minutes. Treated (aluminum nitride powder / ethyl acid phosphate / water = 10
0 parts / 30 parts / 25 parts). Further, 2% of water-repellent silica was dispersed in the aluminum nitride powder. The slurry was filtered and washed with 1000 parts of isopropanol to remove excess ethyl acid phosphate.
This was dried at 80 ° C. for 5 hours, and then pulverized by a jet mill to obtain an aluminum nitride powder. The phosphorus content, water resistance, eluted ionic components and fluidity of the obtained aluminum nitride powder were evaluated in the same manner as in Example 1. The results are shown in Table 1.
Shown in
【００４３】実施例１０ ５Ｌのニーダーで２．４％オルト燐酸水溶液５６．８部
（オルト燐酸１．４部、水５５．４部）に窒化アルミニ
ウム粉末（平均粒径１μｍ）１００部を加え、練り込み
ペースト状とし、３０℃で３０分間処理を行った。この
混合物を１２０℃、８時間乾燥し、乾燥後、ジェットミ
ルで粉砕し、耐水性窒化アルミニウム粉末を得た。更
に、この耐水性窒化アルミニウム粉末に対して撥水性シ
リカを２％添加し、アルミナ製のボールを容量１Ｌの磁
製ポットに入れ、１２０回転で１時間混合粉砕を行い、
窒化アルミニウム粉末を得た。得られた窒化アルミニウ
ム粉末の燐含有量、耐水性、溶出イオン性成分及び流動
性の評価を実施例１と同様に行い、その結果を表１に示
す。Example 10 A 5 L kneader was used to add 100 parts of aluminum nitride powder (average particle size: 1 μm) to 56.8 parts of a 2.4% aqueous solution of orthophosphoric acid (1.4 parts of orthophosphoric acid, 55.4 parts of water). It was made into a kneaded paste and was treated at 30 ° C. for 30 minutes. This mixture was dried at 120 ° C. for 8 hours, and after drying, pulverized by a jet mill to obtain a water-resistant aluminum nitride powder. Furthermore, 2% of water-repellent silica was added to the water-resistant aluminum nitride powder, and a ball made of alumina was put into a porcelain pot having a capacity of 1 L, and mixed and crushed at 120 rotations for 1 hour.
An aluminum nitride powder was obtained. The phosphorus content, water resistance, eluting ionic component and fluidity of the obtained aluminum nitride powder were evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００４４】実施例１１ ２．４％オルト燐酸水溶液５６．８部（オルト燐酸１．
４部、水５５．４部）に予め、窒化アルミニウム粉末に
対して２％の撥水性シリカをメタノールでスラリーにし
て加え、オルト燐酸水溶液中に分散させた。次に前記の
オルト燐酸水溶液に窒化アルミニウム粉末（平均粒径１
μｍ）１００部を加え、５Ｌのニーダーで練り込みペー
スト状とし、３０℃で３０分間処理を行った。この混合
物を１２０℃、８時間乾燥し、更に３００℃で５時間加
熱処理をした後、ジェットミルで粉砕し、窒化アルミニ
ウム粉末を得た。得られた窒化アルミニウム粉末の燐含
有量、耐水性、溶出イオン性成分及び流動性の評価を実
施例１と同様に行い、その結果を表１に示す。Example 11 56.8 parts of a 2.4% aqueous solution of orthophosphoric acid (orthophosphoric acid 1.
(4 parts, water 55.4 parts), 2% of water-repellent silica with respect to the aluminum nitride powder was previously slurried with methanol and dispersed in an orthophosphoric acid aqueous solution. Next, aluminum nitride powder (average particle size: 1) was added to the above-mentioned orthophosphoric acid solution.
μm), and kneaded with a 5 L kneader to form a paste, which was then treated at 30 ° C. for 30 minutes. This mixture was dried at 120 ° C. for 8 hours, heat-treated at 300 ° C. for 5 hours, and then pulverized by a jet mill to obtain aluminum nitride powder. The phosphorus content, water resistance, eluting ionic component and fluidity of the obtained aluminum nitride powder were evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００４５】実施例１２〜１３ 撥水性シリカの添加量を３％、４％に変更した以外は実
施例１１と同様の方法で窒化アルミニウム粉末を得た。
得られた窒化アルミニウム粉末の燐含有量、耐水性、溶
出イオン性成分及び流動性の評価を実施例１と同様に行
い、その結果を表１に示す。Examples 12 to 13 Aluminum nitride powder was obtained in the same manner as in Example 11 except that the amount of water-repellent silica was changed to 3% and 4%.
The phosphorus content, water resistance, eluting ionic component and fluidity of the obtained aluminum nitride powder were evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００４６】実施例１４〜１６ 実施例１１〜１３で得た窒化アルミニウム粉末を１００
℃の純水で洗浄し、濾過乾燥後、ジェットミルで粉砕
し、窒化アルミニウム粉末を得た。得られた窒化アルミ
ニウム粉末の燐含有量、耐水性、溶出イオン性成分及び
流動性の評価を実施例１と同様に行い、その結果を表１
に示す。Examples 14 to 16 The aluminum nitride powder obtained in Examples 11 to 13 was
The resultant was washed with pure water at ℃, filtered and dried, and then pulverized by a jet mill to obtain an aluminum nitride powder. The phosphorus content, water resistance, eluted ionic components and fluidity of the obtained aluminum nitride powder were evaluated in the same manner as in Example 1. The results are shown in Table 1.
Shown in
【００４７】比較例１ 実施例１の撥水性シリカを除いた他は実施例１と同様に
行った。Comparative Example 1 The procedure of Example 1 was repeated except that the water-repellent silica was omitted.
【００４８】得られた耐水性窒化アルミニウム粉末の燐
含有量、耐水性、溶出イオン性成分及び流動性の評価を
実施例１と同様に行い、その結果を表１に示す。The obtained water-resistant aluminum nitride powder was evaluated for phosphorus content, water resistance, leached ionic components and fluidity in the same manner as in Example 1, and the results are shown in Table 1.
【００４９】比較例２〜３ 実施例４及び５の撥水性シリカを除いた他は実施例１と
同様に行った。得られた耐水性窒化アルミニウム粉末の
燐含有量、耐水性、溶出イオン性成分及び流動性の評価
を実施例１と同様に行い、その結果を表１に示す。Comparative Examples 2 to 3 The same procedure as in Example 1 was carried out except that the water-repellent silica of Examples 4 and 5 was omitted. The phosphorus content, water resistance, eluted ionic components and fluidity of the obtained water-resistant aluminum nitride powder were evaluated in the same manner as in Example 1, and the results are shown in Table 1.
【００５０】比較例４ ２．４％オルト燐酸水溶液を２１．５％オルト燐酸水溶
液７７．１部（オルト燐酸１６．６部、水６０．５部）
に変更した以外は、実施例１と同様の方法で窒化アルミ
ニウム粉末を得た。得られた耐水性窒化アルミニウム粉
末の燐含有量、耐水性、溶出イオン性成分及び流動性の
評価を実施例１と同様に行い、その結果を表１に示す。Comparative Example 4 2.4% Orthophosphoric acid aqueous solution was converted to 21.5% orthophosphoric acid aqueous solution 77.1 parts (orthophosphoric acid 16.6 parts, water 60.5 parts)
Except having changed to, the aluminum nitride powder was obtained in the same manner as in Example 1. The phosphorus content, water resistance, eluted ionic components and fluidity of the obtained water-resistant aluminum nitride powder were evaluated in the same manner as in Example 1, and the results are shown in Table 1.
【００５１】実施例１７〜３２ 珪素樹脂１００部に対し、アルミナ粒子とシリカ粒子を
それぞれ１５０部及び実施例１〜１６の操作で得た窒化
アルミニウム粉末１００部を混合し、ニーダーで１０分
間混練して、窒化アルミニウム含有の珪素樹脂組成物を
得た。得られた樹脂組成物を、１５０メッシュのストレ
ーナーを通して押し出し成形したが、ストレーナーを通
らない程の凝集物は認められなかった。Examples 17 to 32 150 parts of alumina particles and silica particles and 100 parts of aluminum nitride powder obtained by the operations of Examples 1 to 16 were mixed with 100 parts of a silicon resin, and kneaded for 10 minutes with a kneader. Thus, a silicon resin composition containing aluminum nitride was obtained. The obtained resin composition was extruded through a 150-mesh strainer, but no agglomerates were observed to such an extent that the resin composition did not pass through the strainer.
【００５２】比較例５〜７ 比較例１〜３の操作で得た耐水性窒化アルミニウム粉末
を用いた以外は実施例１７と同様の方法で窒化アルミニ
ウム含有の珪素樹脂組成物を得た。得られた樹脂組成物
を、１５０メッシュのストレーナーを通して押し出し成
形したが、ストレーナーを通らない凝集物が認められ
た。Comparative Examples 5 to 7 A silicon resin composition containing aluminum nitride was obtained in the same manner as in Example 17 except that the water-resistant aluminum nitride powder obtained by the operations of Comparative Examples 1 to 3 was used. The obtained resin composition was extruded through a 150-mesh strainer, and aggregates not passing through the strainer were observed.
【００５３】[0053]
【表１】 [Table 1]
【００５４】[0054]
【発明の効果】本発明によって得られる窒化アルミニウ
ム粉末は、非常に高い耐水性を有し、更に、イオン性成
分の溶出も抑制できる。また、優れた流動性を付与で
き、凝集体を形成することがないので、樹脂への混練の
際樹脂中に均一に分散することができる。また、放熱が
要求される電子部品の封止材、電子部品の接着材料や積
層基板の成形材料等の樹脂材料用のフィラーとして有用
である。また、耐水性が非常に高く、イオン性成分の溶
出が少ないので、高温耐湿下でも使用でき、従来技術よ
り信頼性の高い製品を得ることができる。さらに、高温
用炉材等の構造用材料として使用する際、成形時にバイ
ンダーとして水系のものを使用しても、加水分解しない
ので、窒化アルミニウム粉末の本来の特性を失うことが
ない。すなわち、本発明の窒化アルミニウム粉末を用い
れば、引火性、且つ有害な有機溶媒をバインダーとして
用いる必要がなく、安価な水が使用できるので、環境面
の改善と安価なコストで高温炉材等を製造できる。The aluminum nitride powder obtained according to the present invention has extremely high water resistance and can suppress the elution of ionic components. In addition, since excellent fluidity can be imparted and no agglomerate is formed, it can be uniformly dispersed in the resin when kneaded into the resin. Further, it is useful as a sealing material for electronic components requiring heat radiation, a filler for resin materials such as an adhesive material for electronic components and a molding material for a laminated substrate. Further, since the water resistance is very high and the ionic components are hardly eluted, it can be used even under high temperature and humidity resistance, and a product more reliable than the prior art can be obtained. Furthermore, when used as a structural material such as a furnace material for high temperature, even if an aqueous binder is used at the time of molding, the binder does not hydrolyze, so that the original characteristics of the aluminum nitride powder are not lost. That is, if the aluminum nitride powder of the present invention is used, it is not necessary to use a flammable and harmful organic solvent as a binder, and inexpensive water can be used. Can be manufactured.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 原田 功 山口県下関市彦島迫町七丁目１番１号 三 井東圧化学株式会社内 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Isao Harada 7-1-1, Hikoshimasako-cho, Shimonoseki-shi, Yamaguchi Pref.
Claims (9)
物で処理された窒化アルミニウム粉末であって、該窒化
アルミニウム粉末に対して該燐酸化合物がＰ ２Ｏ５換算
で０．１〜１０重量％含有することを特徴とする流動性
及び耐水性に優れ、イオン性成分の溶出性の低い窒化ア
ルミニウム粉末。Claims: 1. A phosphorylated composition containing a flow improver.
Aluminum nitride powder treated with
The phosphorous compound is P 2O5Conversion
0.1 to 10% by weight in terms of fluidity
It has excellent water resistance and low elution of ionic components.
Luminium powder.
窒化アルミニウム粉末と流動性改良剤からなる請求項１
記載の窒化アルミニウム粉末。2. A flow improver comprising aluminum nitride powder treated with a phosphate compound in the presence of water and a flow improver.
The aluminum nitride powder as described.
窒化アルミニウム粉末と分散剤存在下、流動性改良剤と
して表面に親油性基を有する無機粉末からなる請求項１
記載の窒化アルミニウム粉末。3. An aluminum nitride powder treated with a phosphoric acid compound in the presence of water and an inorganic powder having a lipophilic group on its surface as a fluidity improving agent in the presence of a dispersant.
The aluminum nitride powder as described.
る無機粉末である請求項１〜３項のいづれか１項に記載
の窒化アルミニウム粉末。4. The aluminum nitride powder according to claim 1, wherein the fluidity improver is an inorganic powder having a lipophilic group on the surface.
タニア、窒化ほう素よりなる群から選ばれる１種以上で
ある請求項１〜４項のいづれか１項に記載の窒化アルミ
ニウム粉末。5. The aluminum nitride powder according to claim 1, wherein the fluidity improver is at least one selected from the group consisting of silica, alumina, titania, and boron nitride.
ウム粉末又は耐水性窒化アルミニウム粉末に対して０．
１〜１０重量％である請求項１〜５項のいづれか１項に
記載の窒化アルミニウム粉末。6. The amount of the fluidity improver to be added to the aluminum nitride powder or the water-resistant aluminum nitride powder is not more than 0.1.
The aluminum nitride powder according to any one of claims 1 to 5, which is 1 to 10% by weight.
ウム化合物とアンモニアを反応することにより得られる
請求項１〜６項のいづれか１項に記載の窒化アルミニウ
ム粉末。7. The aluminum nitride powder according to claim 1, wherein the aluminum nitride powder is obtained by reacting an organic aluminum compound with ammonia.
燐酸化合物で処理し、流動性改良剤を混合することを特
徴とする流動性及び耐水性に優れ、イオン性成分の溶出
性の低い窒化アルミニウム粉末の製造方法。8. An aluminum nitride having excellent fluidity and water resistance and low elution of ionic components, characterized by treating an aluminum nitride powder with a phosphate compound in the presence of water and mixing a fluidity improver. Powder manufacturing method.
燐酸化合物で処理し、分散剤を添加し、流動性改良剤と
して表面に親油性基を有する無機粉末を混合することを
特徴とする流動性及び耐水性に優れ、イオン性成分の溶
出性の低い窒化アルミニウム粉末の製造方法。9. Fluidity characterized by treating an aluminum nitride powder with a phosphate compound in the presence of water, adding a dispersant, and mixing an inorganic powder having a lipophilic group on the surface as a fluidity improver. And a method for producing an aluminum nitride powder having excellent water resistance and low elution of ionic components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13311197A JP3853025B2 (en) | 1997-03-25 | 1997-05-23 | Aluminum nitride powder and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7187197 | 1997-03-25 | ||
| JP9-71871 | 1997-03-25 | ||
| JP13311197A JP3853025B2 (en) | 1997-03-25 | 1997-05-23 | Aluminum nitride powder and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10324510A true JPH10324510A (en) | 1998-12-08 |
| JP3853025B2 JP3853025B2 (en) | 2006-12-06 |
Family
ID=26412992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13311197A Expired - Lifetime JP3853025B2 (en) | 1997-03-25 | 1997-05-23 | Aluminum nitride powder and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3853025B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015133037A1 (en) * | 2014-03-04 | 2015-09-11 | 日東電工株式会社 | Aluminum nitride powder, resin composition, and thermally conductive molded object |
| CN112142474A (en) * | 2020-09-28 | 2020-12-29 | 西华大学 | Preparation method of water-based tape casting high-thermal-conductivity aluminum nitride ceramic substrate |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140061530A1 (en) * | 2011-04-28 | 2014-03-06 | Tokuyama Corporation | Method of manufacturing water resistant aluminium nitride |
-
1997
- 1997-05-23 JP JP13311197A patent/JP3853025B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015133037A1 (en) * | 2014-03-04 | 2015-09-11 | 日東電工株式会社 | Aluminum nitride powder, resin composition, and thermally conductive molded object |
| JP2015166301A (en) * | 2014-03-04 | 2015-09-24 | 日東電工株式会社 | Aluminum nitride powder, resin composition, and thermally conductive molded object |
| CN106068240A (en) * | 2014-03-04 | 2016-11-02 | 日东电工株式会社 | Aluminium nitride powder, resin combination and heat conductivity molded body |
| US9663635B2 (en) | 2014-03-04 | 2017-05-30 | Nitto Denko Corporation | Aluminum nitride powder, resin composition, and thermally conductive molded object |
| CN112142474A (en) * | 2020-09-28 | 2020-12-29 | 西华大学 | Preparation method of water-based tape casting high-thermal-conductivity aluminum nitride ceramic substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3853025B2 (en) | 2006-12-06 |
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