JP2549895B2 - Method for producing fibrous magnesium pyroborate - Google Patents
Method for producing fibrous magnesium pyroborateInfo
- Publication number
- JP2549895B2 JP2549895B2 JP63229489A JP22948988A JP2549895B2 JP 2549895 B2 JP2549895 B2 JP 2549895B2 JP 63229489 A JP63229489 A JP 63229489A JP 22948988 A JP22948988 A JP 22948988A JP 2549895 B2 JP2549895 B2 JP 2549895B2
- Authority
- JP
- Japan
- Prior art keywords
- magnesium
- pyroborate
- source compound
- raw material
- magnesium pyroborate
- 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.)
- Expired - Lifetime
Links
- 239000011777 magnesium Substances 0.000 title claims description 63
- 229910052749 magnesium Inorganic materials 0.000 title claims description 59
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims description 58
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 34
- 239000002994 raw material Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 10
- 230000004907 flux Effects 0.000 claims description 10
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 5
- 239000011565 manganese chloride Substances 0.000 claims description 5
- 235000002867 manganese chloride Nutrition 0.000 claims description 5
- 229940099607 manganese chloride Drugs 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000000835 fiber Substances 0.000 description 24
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 12
- 239000010419 fine particle Substances 0.000 description 10
- 238000000635 electron micrograph Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000001103 potassium chloride Substances 0.000 description 6
- 235000011164 potassium chloride Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- -1 battery diaphragm Substances 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 235000010338 boric acid Nutrition 0.000 description 2
- 229960002645 boric acid Drugs 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- SINKDKBDOQKXDM-UHFFFAOYSA-N manganese;tetrahydrate Chemical compound O.O.O.O.[Mn] SINKDKBDOQKXDM-UHFFFAOYSA-N 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical class O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、繊維状ピロホウ酸マグネシウムの製造方法
に関する。繊維状ピロホウ酸マグネシウムは、プラスチ
ック、金属、セラミックス、コンクリート等の複合強化
材、摩擦材料、過材料、バッテリーの隔膜、顔料、絶
縁材料、耐熱性材料等として有用である。TECHNICAL FIELD The present invention relates to a method for producing fibrous magnesium pyroborate. Fibrous magnesium pyroborate is useful as a composite reinforcing material such as plastic, metal, ceramics, concrete, friction material, excess material, battery diaphragm, pigment, insulating material, and heat resistant material.
従来の技術及びその問題点 従来、繊維状ピロホウ酸マグネシウムは、マグネシウ
ム源化合物、ホウ素源化合物及びフラックスをミキサー
等を用いた機械的方法により乾式混合し、この混合物を
加熱処理して製造されている（例えば特開昭60−204697
号広報参照）。Conventional technology and its problems Conventionally, fibrous magnesium pyroborate is produced by dry-mixing a magnesium source compound, a boron source compound and a flux by a mechanical method using a mixer or the like, and heat-treating this mixture. (For example, JP-A-60-204697
See the public relations).
しかしながら、この方法に従えば、繊維状ピロホウ酸
マグネシウムは、大部分の繊維が塊状に固まった集合塊
（ショット）として生成するを避け得ない。而して斯か
るショットを構成している繊維を解繊する操作において
は、繊維が折損、粉砕されるために、繊維長が短くなっ
たり、繊維の品質及び繊維収率が低下したりする等の問
題が生ずる。However, according to this method, most of the fibrous magnesium pyroborate is inevitably formed as an aggregated mass (shot) in which most of the fibers are solidified into a mass. Thus, in the operation of defibrating the fibers constituting such a shot, the fibers are broken or crushed, so that the fiber length is shortened, the quality of the fibers and the fiber yield are decreased, etc. The problem of occurs.
このような欠点を解消するために、マグネシウム源化
合物、ホウ素源化合物及びフラックスを含有し且つマグ
ネシウム源化合物を微粒化して原料混合物中に均一に分
散させた原料混合溶液を噴霧乾燥し、次いで得られる噴
霧乾燥物を約10℃／分以下の速度で850℃前後まで昇温
し、この温度で処理して、繊維状ピロホウ酸マグネシウ
ムを製造する方法が検討されている（第32回人工鉱物討
論会講演要旨集、第37〜38頁、人工鉱物工学会発行 参
照）。In order to eliminate such drawbacks, a raw material mixed solution containing a magnesium source compound, a boron source compound and a flux, which is atomized and uniformly dispersed in the raw material mixture, is spray-dried and then obtained. A method for producing fibrous magnesium pyroborate by heating the spray-dried product to a temperature of about 850 ° C at a rate of about 10 ° C / min or less and treating it at this temperature has been studied (The 32nd Symposium on Artificial Minerals) (See Proceedings, pages 37-38, published by Society of Artificial Mineral Engineering).
しかるに、この方法では、得られる繊維状ピロホウ酸
マグネシウムの繊維の成長が不充分であって、微粒子の
ものが多く残存しており、更に繊維長が短い等の問題が
あり、改善の余地を残している。However, in this method, the growth of the fibers of the obtained fibrous magnesium pyroborate is insufficient, many fine particles remain, and there is a problem that the fiber length is short, and there is room for improvement. ing.
問題点を解決するための手段 本発明の目的は、ショットがなく、解繊し易く且つ長
さや太さの揃った品質の良好な繊維状ピロホウ酸マグネ
シウムの製造方法を提供することにある。Means for Solving the Problems An object of the present invention is to provide a method for producing fibrous magnesium pyroborate, which has no shots, is easy to be defibrated, and has a uniform length and thickness, and is of good quality.
本発明の他の目的は、繊維長が長く、微粒子状のもの
を殆ど含んでいない繊維状ピロホウ酸マグネシウムを製
造し得る方法を提供することにある。Another object of the present invention is to provide a method for producing a fibrous magnesium pyroborate having a long fiber length and containing almost no fine particles.
本発明の目的は、マグネシウム源化合物、ホウ素源化
合物及びフラックスを含有し且つマグネシウム源化合物
を微粒化して原料混合物中に均一に分散させた原料混合
溶液を噴霧乾燥し、次いで得られる噴霧乾燥物を約10℃
／分以下の速度で850〜950℃まで昇温し、この温度で処
理して繊維状ピロホウ酸マグネシウムを製造するに当
り、上記原料混合溶液中に微粒子状ピロホウ酸マグネシ
ウム及び／又は水酸化マンガンを微粒化して存在させて
おくことにより達成される。The object of the present invention is to spray-dry a raw material mixed solution containing a magnesium source compound, a boron source compound, and a flux and atomizing the magnesium source compound to uniformly disperse the raw material mixture. About 10 ℃
The temperature is increased to 850 to 950 ° C. at a rate of not more than 1 minute / minute, and when the fibrous magnesium pyroborate is produced by treating at this temperature, fine particle magnesium pyroborate and / or manganese hydroxide are added to the raw material mixed solution. It is achieved by atomizing and making it exist.
本発明で用いられるマグネシウム源化合物としては、
従来公知のものを広く使用でき、マグネシウムの酸化
物、水酸化物の他、無機酸、炭酸、硫酸、硝酸、ハロゲ
ン化水素酸のマグネシウム塩のようなマグネシウム化合
物が挙げられる。このような化合物としては、具体的に
は酸化マグネシウム、水酸化マグネシウム、塩基性炭酸
マグネシウム、硫酸マグネシウム、塩化マグネシウム、
臭化マグネシウム等を例示できる。これらは単独で用い
てもよいし、２種以上混合して用いてもよい。As the magnesium source compound used in the present invention,
Conventionally known compounds can be widely used, and in addition to magnesium oxide and hydroxide, magnesium compounds such as inorganic acid, carbonic acid, sulfuric acid, nitric acid, and magnesium salt of hydrohalic acid can be mentioned. As such a compound, specifically, magnesium oxide, magnesium hydroxide, basic magnesium carbonate, magnesium sulfate, magnesium chloride,
Examples include magnesium bromide and the like. These may be used alone or in combination of two or more.
本発明で用いられるホウ素源化合物としても、従来公
知のものを広く使用でき、例えば酸化ホウ素等のホウ素
の酸化物、オルトホウ酸（H3BO3）、四ホウ酸（H2B
4O7）、メタホウ酸（HBO2）等のホウ素の酸素酸、又は
これらのアルカリ金属塩（例えばホウ酸ナトリウム、ピ
ロホウ酸ナトリウム、ピロホウ酸カリウム、メタホウ酸
ナトリウム等）等が挙げられる。これらは単独で用いて
もよいし、２種以上混合して用いてもよい。As the boron source compound used in the present invention, conventionally known compounds can be widely used, and examples thereof include boron oxides such as boron oxide, orthoboric acid (H 3 BO 3 ), tetraboric acid (H 2 B 2
4 O 7 ), oxyboric acid such as metaboric acid (HBO 2 ), or alkali metal salts thereof (for example, sodium borate, sodium pyroborate, potassium pyroborate, sodium metaborate, etc.) and the like. These may be used alone or in combination of two or more.
また本発明で用いられるフラックスとしては、例えば
塩化カリウム、塩化ナトリウム等を挙げることができ、
これらは１種単独で又は混合して使用される。Examples of the flux used in the present invention include potassium chloride and sodium chloride,
These may be used alone or in combination.
上記マグネシウム源化合物、ホウ素源化合物及びフラ
ックスの配合割合としては、特に限定されるものではな
いが、通常マグネシウム源化合物とホウ素源化合物のモ
ル比が1:4から1:1であり且つフラックスが全重量に基づ
き10〜95重量％となるように３者を配合するのがよい。
本発明では、特にマグネシウム源化合物、ホウ素源化合
物及びフラックスを2:3:7（モル比）の割合で配合する
のが好適である。The mixing ratio of the magnesium source compound, the boron source compound and the flux is not particularly limited, but usually the molar ratio of the magnesium source compound and the boron source compound is 1: 4 to 1: 1 and the total flux. It is advisable to mix the three components so that the amount is 10 to 95% by weight based on the weight.
In the present invention, it is particularly preferable to mix the magnesium source compound, the boron source compound and the flux at a ratio of 2: 3: 7 (molar ratio).
本発明では、上記マグネシウム源化合物を微粒化して
原料混合物中に均一に分散させておくことが必要であ
る。マグネシウム源化合物の微粒化・均一分散化の方法
としては、例えば下記Ａ、Ｂの方法を挙げることができ
る。In the present invention, it is necessary to atomize the magnesium source compound and uniformly disperse it in the raw material mixture. Examples of the method for atomizing and uniformly dispersing the magnesium source compound include the following methods A and B.
方法A: 不溶性のマグネシウム源化合物を酸の作用により可溶
化し、これを水に溶解して水溶液としたもの、或は可溶
性のマグネシウム源化合物（例えば可溶性マグネシウム
塩）を水に溶解して水溶液としたものに、アルカリを加
えて中和すると、コロイド状の不溶性マグネシウム源化
合物を懸濁液の形態で得ることができる。該コロイド状
不溶性マグネシウム源化合物の懸濁液に、ホウ素源化合
物及びフラックスを添加し、混合すると、マグネシウム
源化合物が微粒化、均一分散化された原料混合物を得る
ことができる。Method A: An insoluble magnesium source compound is solubilized by the action of an acid and dissolved in water to give an aqueous solution, or a soluble magnesium source compound (for example, a soluble magnesium salt) is dissolved in water to give an aqueous solution. When an alkali is added to the prepared product to neutralize it, a colloidal insoluble magnesium source compound can be obtained in the form of a suspension. When the boron source compound and the flux are added to and mixed with the suspension of the colloidal insoluble magnesium source compound, a raw material mixture in which the magnesium source compound is atomized and uniformly dispersed can be obtained.
方法B: 塗料調整の際、高分散させるためによく用いられるデ
ィスパー分散、ボールミル分散、グレインミル分散等の
方法で、不溶性のマグネシウム源化合物を水に分散さ
せ、得られるマグネシウム源化合物の高分散スラリー液
中にホウ素源化合物及びフラックスを添加し、混合する
と、マグネシウム源化合物が微粒化、均一分散化された
原料混合物を得ることができる。Method B: Dispersion, ball mill dispersion, grain mill dispersion, etc., which are often used for high dispersion during paint preparation, are used to disperse an insoluble magnesium source compound in water and obtain a highly dispersed slurry of the magnesium source compound. When the boron source compound and the flux are added to the liquid and mixed, a raw material mixture in which the magnesium source compound is atomized and uniformly dispersed can be obtained.
本発明においては、上記原料混合溶液中に、微粒子状
ピロホウ酸マグネシウム及び／又は水酸化マンガンを微
粒化して存在させておくことが必要である。微粒子ピロ
ホウ酸マグネシウムの量は、Mgに対して通常１〜20モル
％程度、好ましくは５〜15モル％程度がよく、また水酸
化マンガンの量は、Mgに対しMn2+換算で通常0.2〜２モ
ル％程度、好ましくは0.5〜1.5モル％程度がよい。In the present invention, it is necessary to atomize fine particle magnesium pyroborate and / or manganese hydroxide in the above-mentioned raw material mixed solution. The amount of fine particles of magnesium pyroborate is usually 1 to 20 mol% or so with respect to Mg, preferably 5 to 15 mol% or so, and the amount of manganese hydroxide is usually 0.2 to 10 in terms of Mn 2+ with respect to Mg. It is about 2 mol%, preferably about 0.5 to 1.5 mol%.
微粒子状ピロホウ酸マグネシウムの添加時期は、上記
Ａ法ではアルカリを加えて中和し、コロイド状の不溶性
マグネシウム源化合物を得た後に行なうのがよい。また
Ｂ法では特に限定されるものではない。In the method A, it is preferable to add an alkali to neutralize the particulate magnesium pyroborate to obtain a colloidal insoluble magnesium source compound. The method B is not particularly limited.
水酸化マンガンについては、Ａ法ではマグネシウム源
化合物と一緒に塩化マンガンを酸に溶解し、アルカリで
中和して水酸化マンガンとして使用され、またＢ法では
水酸化マンガンとして添加されるが、その添加時期は特
に限定されるものではない。Regarding manganese hydroxide, in method A, manganese chloride is dissolved in an acid together with a magnesium source compound and neutralized with an alkali to be used as manganese hydroxide, and in method B, it is added as manganese hydroxide. The timing of addition is not particularly limited.
本発明では、次に上記で得られる原料混合溶液を噴霧
乾燥する。噴霧乾燥手段としては、特に限定がなく、従
来の方法を広く適用できる。In the present invention, the raw material mixed solution obtained above is then spray-dried. The spray drying means is not particularly limited, and conventional methods can be widely applied.
本発明では、次いで得られる噴霧乾燥物を約10℃／分
以下の速度で850〜950℃まで昇温し、この温度で処理す
る。本発明では、特に750℃前後までは、約10℃／分の
速度で昇温し、この温度以上になると、約１℃／分の速
度で昇温するのが望ましい。昇温速度が10℃／分より極
端に速くなると、マグネシウムパイロボレートの生成及
び結晶化が急激に進行するため、結晶成長が不定方向に
起り、長さ、太さの揃った繊維の成長を阻害し、その結
果本発明の所期の目的が達成され得なくなるので、好ま
しくない。また加熱処理の温度は850〜950℃であること
を要し、その温度での処理時間は１〜５時間程度が望ま
しい。650℃や750℃での加熱処理では、微粒子状ピロホ
ウ酸マグネシウムが生成するに止まり、本発明の如き長
さや太さの揃った繊維状ピロホウ酸マグネシウムを得る
ことは不可能である。In the present invention, the resulting spray-dried product is then heated to 850 to 950 ° C at a rate of about 10 ° C / minute or less and treated at this temperature. In the present invention, it is desirable to raise the temperature at a rate of about 10 ° C./min up to around 750 ° C., and to raise the temperature at a rate of about 1 ° C./min above this temperature. When the heating rate is much faster than 10 ° C / min, the generation and crystallization of magnesium pyroborate will proceed rapidly, causing the crystal growth to occur in an indefinite direction and hindering the growth of fibers of uniform length and thickness. However, this is not preferable because the intended purpose of the present invention cannot be achieved. Further, the temperature of the heat treatment needs to be 850 to 950 ° C., and the treatment time at that temperature is preferably about 1 to 5 hours. By heat treatment at 650 ° C. or 750 ° C., only fine particles of magnesium pyroborate are produced, and it is impossible to obtain fibrous magnesium pyroborate having uniform length and thickness as in the present invention.
発明の効果 本発明の方法によれば、ショットがなく、解繊し易
く、且つ長さや太さの揃った品質の良好な繊維状ピロホ
ウ酸マグネシウムを容易に得ることができる。しかも本
発明の方法で得られる繊維状ピロホウ酸マグネシウム
は、繊維の成長が充分であるため、微粒子を殆んど含ん
でおらず、また繊維長さが長いものである。斯かる長さ
及び太さの揃った繊維は、優れた強化性能を発揮する等
の利点を有し、それ故本発明方法により得られる繊維状
ピロホウ酸マグネシウムは工業的利用価値が大きい。EFFECTS OF THE INVENTION According to the method of the present invention, fibrous magnesium pyroborate having no shots, easy to be defibrated, and good quality with uniform length and thickness can be easily obtained. Moreover, the fibrous magnesium pyroborate obtained by the method of the present invention contains almost no fine particles and has a long fiber length because the growth of the fibers is sufficient. Such fibers having uniform length and thickness have advantages such as exhibiting excellent reinforcing performance, and therefore the fibrous magnesium pyroborate obtained by the method of the present invention has great industrial utility value.
実施例 以下に実施例及び比較例を掲げて本発明をより一層明
らかにする。Examples The present invention will be further clarified below with reference to Examples and Comparative Examples.
実施例１ 酸化マグネシウム8.06g（0.2モル）及び塩化マンガン
・４水塩0.2g（１ミリモル）に4M−塩酸水溶液0.1を
添加して溶解した後、溶液を撹拌しながら2M−水酸化カ
リウム水溶液0.2を徐々に添加して中和し、コロイド
状の水酸化マグネシウムと水酸化マンガンとを生成させ
る。次いでこれにオルトホウ酸18.55g（0.3モル）及び
塩化カリウム22.37g（0.3モル）を添加し、撹拌して溶
解させる。この混合溶液を、ヤマト科学ミニスプレーDL
−21により噴霧乾燥して、Mg、Ｂ、KCl及び触媒Mnを含
んだ原料混合物を製造した。この原料混合物は、電子顕
微鏡による観察の結果、直径３〜10μｍ程度の微粒子
で、その中にMgはほぼ均一に分布していた。Example 1 8.06 g (0.2 mol) of magnesium oxide and 0.2 g (1 mmol) of manganese chloride.tetrahydrate were added and dissolved with 0.1 M of 4M-hydrochloric acid, and then the solution was stirred and 0.2 M of 2M-potassium hydroxide was added. Is gradually added to neutralize and form colloidal magnesium hydroxide and manganese hydroxide. Then, 18.55 g (0.3 mol) of orthoboric acid and 22.37 g (0.3 mol) of potassium chloride are added thereto, and they are dissolved by stirring. This mixed solution is Yamato Scientific Mini Spray DL
It was spray dried by -21 to prepare a raw material mixture containing Mg, B, KCl and catalyst Mn. As a result of observation with an electron microscope, this raw material mixture was fine particles with a diameter of about 3 to 10 μm, and Mg was distributed almost uniformly therein.
上記原料混合物の50gをアルミナるつぼに充填し、950
℃まで昇温し（室温〜750℃の温度領域での昇温速度10
℃／分、750〜950℃の温度領域での昇温速度１℃／
分）、950℃に３時間保ち、加熱処理した。焼成物は、
熱水中で煮沸してKClを溶解除去した後、水洗、乾燥し
た。その結果直径が0.3μｍ前後、平均繊維長30μｍの
ショットを含まない所望の繊維状ピロホウ酸マグネシウ
ム8.7gが得られた。この繊維状ピロホウ酸マグネシウム
の電子顕微鏡写真を第１図に示す。尚、該繊維の平均繊
維長は、ルーゼックスII〔東洋インキ製造社製〕を用い
て測定したものであり、これは以下の実施例においても
同じである。Alumina crucible was filled with 50 g of the above raw material mixture, and 950
The temperature is raised to ℃ (room temperature to 750 ℃ in the temperature range 10
℃ / min, temperature rising rate in the temperature range of 750-950 ℃ 1 ℃ /
Min) and kept at 950 ° C. for 3 hours and heat-treated. The fired product is
After boiling in hot water to dissolve and remove KCl, it was washed with water and dried. As a result, 8.7 g of desired fibrous magnesium pyroborate having a diameter of about 0.3 μm and an average fiber length of 30 μm and containing no shot was obtained. An electron micrograph of this fibrous magnesium pyroborate is shown in FIG. The average fiber length of the fibers was measured using Luzex II (manufactured by Toyo Ink Mfg. Co., Ltd.), and this is the same in the following examples.
実施例２ 塩化マンガン・４水塩0.5g（2.4ミリモル）を用いる
以外は、上記実施例１と同じ条件で噴霧乾燥、加熱処理
を行なったところ、ショットを含まず、直径0.3μｍ前
後、平均繊維長29μｍの所望の繊維状ピロホウ酸マグネ
シウム8.7gが得られた。Example 2 Spray drying and heat treatment were carried out under the same conditions as in Example 1 except that 0.5 g (2.4 mmol) of manganese chloride / tetrahydrate was used. No shot was included, a diameter was around 0.3 μm, and an average fiber was used. 8.7 g of the desired fibrous magnesium pyroborate having a length of 29 μm were obtained.
実施例３ 塩化マグネシウム（MgCl2・6H2O）40.64g（0.2モ
ル）、塩化マンガン・４水塩0.2g（１ミリモル）及び塩
化カリウム22.37g（0.3モル）の混合水溶液0.1、ホウ
砂（Na2B4O7・10H2O）28.59g（0.075モル）の水溶液0.2
、次いで2.5M−水酸化ナトリウム水溶液0.1を撹拌
しながら徐々に添加した後、上記実施例１と同じ条件で
噴霧乾燥、加熱処理を行なった。生成物は、ショットを
含まず、直径0.3μｍ前後、平均繊維長31μｍの所望の
繊維状ピロホウ酸マグネシウムであった。Example 3 Magnesium chloride (MgCl 2 .6H 2 O) 40.64 g (0.2 mol), manganese chloride tetrahydrate 0.2 g (1 mmol) and potassium chloride 22.37 g (0.3 mol) mixed aqueous solution 0.1, borax (Na 2 B 4 O 7・ 10H 2 O) 28.59 g (0.075 mol) aqueous solution 0.2
Then, 0.1% of 2.5 M sodium hydroxide aqueous solution was gradually added with stirring, and then spray drying and heat treatment were performed under the same conditions as in Example 1 above. The product was the desired fibrous magnesium pyroborate without shots and having a diameter of around 0.3 μm and an average fiber length of 31 μm.
実施例４ 水酸化マグネシウム23.32g（0.4モル）及び微粒子ピ
ロホウ酸マグネシウム（Mg2B2O5）0.3g（２ミリモル）
を水0.5中に分散させ、ボールミルにより高分散させ
たスラリー液を調製した。調製されたスラリー液中の固
形物の粒子径は３μｍ以下であった。得られたスラリー
中にオルトホウ酸37.1g（0.6モル）及び塩化カリウム4
4.74g（0.6モル）を添加し、撹拌して溶解させた後、90
0℃まで昇温する以外は、上記実施例１と同じ条件で噴
霧乾燥、加熱処理を行なった。生成物は、ショットを含
まず、直径１〜1.5μｍ前後、平均繊維長30μｍの所望
の繊維状ピロホウ酸マグネシウムであった。この繊維状
ピロホウ酸マグネシウムの電子顕微鏡写真を第２図に示
す。Example 4 23.32 g (0.4 mol) of magnesium hydroxide and 0.3 g (2 mmol) of fine particle magnesium pyroborate (Mg 2 B 2 O 5 ).
Was dispersed in 0.5 of water and highly dispersed by a ball mill to prepare a slurry liquid. The particle size of the solid matter in the prepared slurry liquid was 3 μm or less. In the resulting slurry, 37.1 g (0.6 mol) orthoboric acid and 4 potassium chloride were added.
After adding 4.74 g (0.6 mol) and stirring to dissolve, 90
Spray drying and heat treatment were performed under the same conditions as in Example 1 except that the temperature was raised to 0 ° C. The product was the desired fibrous magnesium pyroborate, without shots, having a diameter of around 1-1.5 μm and an average fiber length of 30 μm. An electron micrograph of this fibrous magnesium pyroborate is shown in FIG.
実施例５ 微粒子ピロホウ酸マグネシウムを0.6g（４ミリモル）
使用し、且つ850℃まで昇温する以外は、上記実施例と
同じ条件で噴霧乾燥、加熱処理を行なった。生成物は、
ショットを含まず、直径0.6μｍ前後、平均繊維長25μ
ｍの所望の繊維状ピロホウ酸マグネシウムであった。こ
の繊維状ピロホウ酸マグネシウムの電子顕微鏡写真を第
３図に示す。Example 5 0.6 g (4 mmol) of fine particles of magnesium pyroborate
Spray drying and heat treatment were carried out under the same conditions as in the above-mentioned example except that the composition was used and the temperature was raised to 850 ° C. The product is
Not including shots, diameter around 0.6μm, average fiber length 25μ
m of the desired fibrous magnesium pyroborate. An electron micrograph of this fibrous magnesium pyroborate is shown in FIG.
比較例 塩化マンガン・４水塩を添加しない以外は、実施例１
と同じ条件で処理した。得られた生成物は、板状・柱状
であった。この生成物の電子顕微鏡写真を第４図に示
す。Comparative Example Example 1 except that manganese chloride / tetrahydrate was not added.
It was processed under the same conditions. The obtained product was plate-shaped / columnar. An electron micrograph of this product is shown in FIG.
第１図は、実施例１で得られた繊維状ピロホウ酸マグネ
シウムの繊維の形状を示す電子顕微鏡写真を示したもの
である。第２図は、実施例４で得られた繊維状ピロホウ
酸マグネシウムの繊維の形状を示す電子顕微鏡写真を示
したものである。第３図は、実施例５で得られた繊維状
ピロホウ酸マグネシウムの繊維の形状を示す電子顕微鏡
写真を示したものである。第４図は、比較例で得られた
ピロホウ酸マグネシウムの繊維の形状を示す電子顕微鏡
写真を示したものである。FIG. 1 is an electron micrograph showing the shape of the fibrous magnesium pyroborate fibers obtained in Example 1. FIG. 2 is an electron micrograph showing the shape of the fibrous magnesium pyroborate fiber obtained in Example 4. FIG. 3 is an electron micrograph showing the fiber shape of the fibrous magnesium pyroborate obtained in Example 5. FIG. 4 is an electron micrograph showing the shape of the magnesium pyroborate fiber obtained in the comparative example.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小川 淳 徳島県徳島市川内町加賀須野463番地 大塚化学株式会社徳島工場内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Atsushi Ogawa 463, Kagasuno, Kawauchi Town, Tokushima City, Tokushima Prefecture Otsuka Chemical Co., Ltd. Tokushima Plant
Claims (2)
びフラックスを含有し且つマグネシウム源化合物を微粒
化して原料混合物中に均一に分散させた原料混合溶液を
噴霧乾燥し、次いで得られる噴霧乾燥物を約10℃／分以
下の速度で850〜950℃まで昇温し、この温度で処理して
繊維状ピロホウ酸マグネシウムを製造するに当り、上記
原料混合溶液中に微粒子状ピロホウ酸マグネシウム及び
／又は水酸化マンガンを微粒化して存在させておくこと
を特徴とする繊維状ピロホウ酸マグネシウムの製造方
法。1. A raw material mixed solution containing a magnesium source compound, a boron source compound, and a flux, which is atomized and uniformly dispersed in a raw material mixture, is spray-dried, and then the resulting spray-dried product is dried. When producing fibrous magnesium pyroborate by raising the temperature to 850 to 950 ° C at a rate of 10 ° C / min or less, in the above raw material mixed solution, finely divided magnesium pyroborate and / or hydroxide are added. A method for producing fibrous magnesium pyroborate, characterized in that manganese is atomized and allowed to exist.
て水溶液中にて加水分解により生成されたものである請
求項記載の方法。2. The method according to claim 1, wherein the manganese hydroxide is produced by hydrolyzing manganese chloride in an aqueous solution as a raw material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63229489A JP2549895B2 (en) | 1988-09-12 | 1988-09-12 | Method for producing fibrous magnesium pyroborate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63229489A JP2549895B2 (en) | 1988-09-12 | 1988-09-12 | Method for producing fibrous magnesium pyroborate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0275351A JPH0275351A (en) | 1990-03-15 |
| JP2549895B2 true JP2549895B2 (en) | 1996-10-30 |
Family
ID=16892966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63229489A Expired - Lifetime JP2549895B2 (en) | 1988-09-12 | 1988-09-12 | Method for producing fibrous magnesium pyroborate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2549895B2 (en) |
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1988
- 1988-09-12 JP JP63229489A patent/JP2549895B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH0275351A (en) | 1990-03-15 |
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