JP2610004B2 - Glass beads - Google Patents
Glass beadsInfo
- Publication number
- JP2610004B2 JP2610004B2 JP63105832A JP10583288A JP2610004B2 JP 2610004 B2 JP2610004 B2 JP 2610004B2 JP 63105832 A JP63105832 A JP 63105832A JP 10583288 A JP10583288 A JP 10583288A JP 2610004 B2 JP2610004 B2 JP 2610004B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- glass beads
- beads
- chemical durability
- exceeds
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、粉粒体の粉砕・分散に用いられるガラスビ
ーズに関する。Description: TECHNICAL FIELD The present invention relates to glass beads used for pulverizing and dispersing powders.
〔従来の技術〕 一般に顔料や磁気記録用磁性粉末等の微粉砕または分
散剤中への均質な分散を行う方法にガラスビーズを使用
したサンドミル等による方法が知られている。たとえ
ば、粉体を分散剤中に分散させる工程では、容器内に目
的とする製品の原料粉体と分散剤を収容し、これにガラ
スビーズを加えて高速回転する撹拌子で撹拌して、内容
物相互の衝突・摩擦によって分散をはかる。ここでガラ
スビーズは粉体と分散剤の分離を防ぎ、衝突・撹拌を助
勢して均質化を促進する作用をする。[Prior Art] Generally, a method using a sand mill or the like using glass beads has been known as a method for finely pulverizing pigments or magnetic powder for magnetic recording or the like and uniformly dispersing them in a dispersant. For example, in the step of dispersing the powder in the dispersant, the raw material powder of the target product and the dispersant are contained in a container, glass beads are added thereto, and the mixture is stirred by a high-speed rotating stirrer. Dispersion is measured by collision and friction between objects. Here, the glass beads serve to prevent separation of the powder and the dispersant, and to promote collision and stirring to promote homogenization.
従来、この種のガラスビーズには、主としてソーダ石
灰系のガラスからなるビーズが使用されてきたが、ガラ
ス組成中にアルカリ酸化物を多量に含有しているため、
使用時にアルカリ成分が溶出してpH等の条件に変化をも
たらし、製品特性に影響を与えるという問題があった。
また、ガラスビーズ自体の機械的強度が低く、摩耗損失
が激しい。このためガラスビーズの破砕や摩耗によって
生じる微小ガラス片が製品粉末中に混入し、製品の品質
を著しく低下させる。Conventionally, as glass beads of this kind, beads mainly made of soda-lime glass have been used, but since the glass composition contains a large amount of alkali oxide,
At the time of use, there has been a problem that alkaline components are eluted to change conditions such as pH, thereby affecting product characteristics.
In addition, the mechanical strength of the glass beads itself is low, and the wear loss is severe. For this reason, fine glass fragments generated by crushing or abrasion of the glass beads are mixed into the product powder, and the quality of the product is significantly reduced.
また、ガラスからのアルカリ溶出を避けるため無アル
カリガラスからなるビーズも使用されていた。Also, beads made of non-alkali glass have been used to avoid alkali elution from the glass.
従来の無アルカリガラスビーズは、ガラスの溶融性を
良好にするためアルカリ土類金属酸化物を比較的多量に
含んでいるのが普通である。ガラス中においてアルカリ
土類金属は２価の陽イオンとして存在し、その含有量が
多いとガラス網目構造の結合は相対的に弱められること
になる。このため、ガラスビーズの摩耗が早く、アルカ
リ土類金属が溶出するなど、ソーダ石灰系のガラスビー
ズと同様の問題点を有していた。Conventional alkali-free glass beads usually contain a relatively large amount of alkaline earth metal oxide in order to improve the melting property of the glass. In the glass, the alkaline earth metal exists as a divalent cation, and when the content thereof is large, the bonding of the glass network structure is relatively weakened. For this reason, the glass beads have the same problems as soda-lime glass beads, such as rapid wear of the glass beads and elution of the alkaline earth metal.
本発明は上記事情を考慮してなされたもので、耐摩耗
性および化学的耐久性に優れ、しかも機械的強度の大き
なガラスビーズを提供することを目的とする。The present invention has been made in view of the above circumstances, and an object of the present invention is to provide glass beads having excellent abrasion resistance and chemical durability and high mechanical strength.
本発明は、SiO2,Al2O3,B2O3を基本成分とするガラス
で、ガラスを構成する陽イオン原子の作用に着目してア
ルカリ土類金属酸化物の含有量を少量に限定して上記目
的を達成したものである。The present invention is a glass containing SiO 2 , Al 2 O 3 , and B 2 O 3 as basic components, and limits the content of alkaline earth metal oxide to a small amount by focusing on the action of cation atoms constituting the glass. Thus, the above object has been achieved.
すなわち、本発明はモル百分率で、SiO2 43〜58％,T
iO2 ３〜15％,ZrO2 ０〜５％,TiO2＋ZrO2 ３〜15％,
B2O3 ６〜30％,Al2O3 ７〜20％,Bi2O3 ０〜５％,La2
O3 ０〜５％,Al2O3＋Bi2O3＋La2O3 ７〜20％,CaO ０
〜10％,BaO ０〜10％,MgO ０〜10％,SrO ０〜10％,C
aO＋BaO＋MgO＋SrO ２〜13％,Na2O＋K2O＋Li2O ０〜
0.7％からなる組成を有し、かつガラスを構成する陽イ
オン原子の平均原子価が3.41〜3.65の範囲にあることを
特徴とするガラスビーズである。That is, the present invention relates to SiO 2 43-58%, T
iO 2 3-15%, ZrO 2 0-5%, TiO 2 + ZrO 2 3-15%,
B 2 O 3 6~30%, Al 2 O 3 7~20%, Bi 2 O 3 0~5%, La 2
O 3 0-5%, Al 2 O 3 + Bi 2 O 3 + La 2 O 3 7-20%, CaO 0
-10%, BaO 0-10%, MgO 0-10%, SrO 0-10%, C
aO + BaO + MgO + SrO 2-13%, Na 2 O + K 2 O + Li 2 O 0
Glass beads having a composition of 0.7% and an average valence of cation atoms constituting the glass in a range of 3.41 to 3.65.
次に上記組成範囲を限定した理由について説明する。 Next, the reason for limiting the above composition range will be described.
SiO2はガラス網目を形成する基本成分であるが、43％
未満ではガラスの強度および化学的耐久性が低下するう
え、ガラス化しにくくビーズ成形時に失透を生じる。ま
た58％を越えると溶融性が著しく悪下し、高温粘性が高
くなってビーズ成形が困難となる。TiO2はガラスの化学
的耐久性を向上させる効果があるが、３％未満ではその
効果が得られず、15％を越えると溶融性が悪化する。Zr
O2はTiO2と同様の効果があり、TiO2の一部に置換して用
いることもできるが、５％を越えると溶融性が悪くな
る。よって、TiO2とZrO2は合量で３〜15％の範囲内にあ
ることが好ましい。B2O3は溶融性を改善する効果がある
が、６％未満ではその効果がなく、30％を越えると化学
的耐久性が劣化する。Al2O3はガラスの化学的耐久性を
向上させ、失透を抑制するが、７％未満ではその効果が
得られず、20％を越えると溶融性が悪化する。Al2O3の
一部をBi2O3,La2O3で置換しても同様の効果が得られる
が、各々５％を越えると溶融性が悪くなり好ましくな
い。アルカリ土類金属酸化物はガラスの溶融性を改善す
るが、その合量が２％未満では溶融性が改善されず、各
成分またはその合量が上記範囲を越えると化学的耐久性
が劣化し、ガラスからのアルカリ土類金属成分の溶出が
生じる。アルカリ金属酸化物はガラス原料中の不純物と
して混入するが、その合量が0.7％以下であれば、ガラ
スからのアルカリ溶出は無視できる。SiO 2 is a basic component that forms a glass network, but 43%
If it is less than 10, the strength and chemical durability of the glass are reduced, and the glass is hardly vitrified and devitrification occurs during bead molding. On the other hand, if it exceeds 58%, the melting property is remarkably deteriorated, the viscosity at high temperature becomes high, and it becomes difficult to form beads. TiO 2 has the effect of improving the chemical durability of glass, but if less than 3%, the effect cannot be obtained, and if it exceeds 15%, the meltability deteriorates. Zr
O 2 has the same effect as TiO 2, and can be used by substituting a part of TiO 2. However, if it exceeds 5%, the meltability deteriorates. Therefore, the total amount of TiO 2 and ZrO 2 is preferably in the range of 3 to 15%. B 2 O 3 has the effect of improving the meltability, but if it is less than 6%, it has no effect, and if it exceeds 30%, the chemical durability deteriorates. Al 2 O 3 improves the chemical durability of the glass and suppresses the devitrification. However, if it is less than 7%, the effect cannot be obtained, and if it exceeds 20%, the melting property deteriorates. The same effect can be obtained by substituting a part of Al 2 O 3 with Bi 2 O 3 or La 2 O 3 , but if each exceeds 5%, the meltability deteriorates, which is not preferable. Alkaline earth metal oxides improve the melting property of glass, but if the total amount is less than 2%, the melting property will not be improved. If the total amount of each component or the total amount exceeds the above range, chemical durability will deteriorate. Elution of alkaline earth metal components from glass occurs. The alkali metal oxide is mixed as an impurity in the glass raw material. If the total amount is 0.7% or less, alkali elution from the glass can be ignored.
また、ガラスを構成する陽イオン原子の平均原子価が
高くなる方がガラスの網目構造が強固になると考えられ
るが、モル含有比率における平均原子価が3.65を越える
とガラスの溶融性が著しく悪化し、3.41未満ではガラス
の化学的耐久性・機械的強度が低下する。Also, it is thought that the higher the average valence of the cation atoms constituting the glass, the stronger the network structure of the glass.However, if the average valence in the molar content ratio exceeds 3.65, the melting property of the glass is significantly deteriorated. If it is less than 3.41, the chemical durability and mechanical strength of the glass decrease.
本発明の実施例を次表に示す。表中、ガラス組成はモ
ル百分率で示してある。Examples of the present invention are shown in the following table. In the table, the glass composition is shown in mole percentage.
下表のガラスは、いずれも所定の酸化物組成が得られ
るように原料を調合・溶融し、溶融状態にあるガラスを
高速度で回転する円板の上面に連続的に流下させ、円板
との接触時に生じる衝撃波と円板の遠心力によってガラ
スを分散・飛散させて空中での表面張力で球状に成形し
たものである。The glasses in the table below are prepared by mixing and melting the raw materials so as to obtain the specified oxide composition, and the glass in the molten state is allowed to continuously flow down on the upper surface of the rotating disk at a high speed. The glass is dispersed and scattered by a shock wave generated at the time of contact with the disk and the centrifugal force of the disk, and is formed into a spherical shape by surface tension in the air.
ガラスビーズの粒径は円板の回転速度を変化させるこ
とにより任意に調整することができるが、ある一定範囲
の粒径分布を有して製造されるため所望粒径のガラスビ
ーズを得るには篩分による選別を行う。 The particle size of the glass beads can be arbitrarily adjusted by changing the rotation speed of the disk.However, since the glass beads are manufactured with a certain range of particle size distribution, it is necessary to obtain glass beads having a desired particle size. Sort by sieving.
本発明のガラスビーズを分散促進材としてサンドミル
などに使用する場合には、ビーズの直径を0.7〜4mmの範
囲に限定することが望ましい。この理由は、ビーズの直
径が0.7mmより小さいとビーズが軽量なためミーリング
時に運動エネルギーが不足し粉砕効果が劣り、直径4mm
を越えるとビーズ相互の間隙が大きく、かつ衝突回数も
少なくなり分散効果が低下するためである。When the glass beads of the present invention are used as a dispersion accelerator in a sand mill or the like, it is desirable to limit the diameter of the beads to a range of 0.7 to 4 mm. The reason for this is that if the diameter of the beads is smaller than 0.7 mm, the beads are lightweight, so the kinetic energy is insufficient during milling and the crushing effect is inferior.
This is because if the value exceeds, the gap between the beads is large, the number of collisions is reduced, and the dispersion effect is reduced.
上記のようにして得たガラスビーズについて、耐摩耗
性，圧縮強度，耐水性を測定した。その結果を表中に示
す。これらの特性について、耐摩耗性は、２のサン
ドミルに2Kgのガラスビーズと水を収容し、撹拌子を300
0回／分で回転させて48時間後のガラスビーズの摩耗減
量を百分率で示した値、圧縮強度はオードグラフ圧縮
試験装置による圧縮破砕強度測定値、耐水性は大阪工
業試験所法による溶出物の中和滴定に使用した1/100N・
HCl溶液のml数である。The abrasion resistance, compressive strength, and water resistance of the glass beads obtained as described above were measured. The results are shown in the table. Regarding these properties, the abrasion resistance was as follows: 2 kg of glass beads and water were placed in a 2 sand mill, and the stirrer was
A value indicating the abrasion loss of glass beads after 48 hours by rotating at 0 times / minute as a percentage, compressive strength is measured by compressive crushing strength using an autograph compression tester, and water resistance is eluted by the Osaka Industrial Laboratory. 1 / 100N used for neutralization titration of
The number of ml of HCl solution.
これらの測定結果から明らかなように本発明に係る実
施例のガラスビーズは、耐摩耗性が従来例の２〜４倍と
大幅に改善され、耐水性によって代表される化学的耐久
性も良好で、分散時におけるアルカリまたはアルカリ土
類金属成分の溶出によるpH値の変化はほとんどなくなっ
た。As is clear from these measurement results, the glass beads of the examples according to the present invention have significantly improved abrasion resistance 2 to 4 times that of the conventional example, and also have good chemical durability represented by water resistance. In addition, there was almost no change in pH value due to elution of the alkali or alkaline earth metal component during dispersion.
以上のように本発明のガラスビーズは、耐摩耗性，機
械的強度，化学的耐久性等において従来のガラスビーズ
よりすぐれているので、粉粒体の分散促進材として使用
する場合に次のような効果がある。As described above, the glass beads of the present invention are superior to conventional glass beads in abrasion resistance, mechanical strength, chemical durability, and the like. Has a significant effect.
耐摩耗性にすぐれ、ガラスビーズの寿命が長く、長期
間連続使用できる。Excellent abrasion resistance, long life of glass beads, and can be used continuously for a long time.
機械的強度が大でガラスビーズ自体の破砕が生じにく
いので、粉粒体へのガラスビーズ破片の混入を防止する
ことができ、製品の品質が向上する。Since the mechanical strength is large and the glass beads themselves are hard to be crushed, it is possible to prevent glass beads fragments from being mixed into the granular material, thereby improving the quality of the product.
化学的耐久性にすぐれているので、アルカリ性または
酸性状態での使用にも安定で、分散剤の化学的・物理的
変化を起さない。Because of its excellent chemical durability, it is stable even when used in an alkaline or acidic state, and does not cause any chemical or physical change of the dispersant.
Claims (1)
〜15％,ZrO2 ０〜５％,TiO2＋ZrO2 ３〜15％,B2O3
６〜30％,Al2O3 ７〜20％,Bi2O3 ０〜５％,La2O3 ０
〜５％,Al2O3＋Bi2O3＋La2O3 ７〜20％,CaO ０〜10
％,BaO ０〜10％,MgO ０〜10％,SrO ０〜10％,CaO＋
BaO＋MgO＋SrO ２〜13％,Na2O＋K2O＋Li2O ０〜0.7％
からなる組成を有し、かつガラスを構成する陽イオン原
子の平均原子価が3.41〜3.65の範囲にあることを特徴と
するガラスビーズ。(1) SiO 2 43-58%, TiO 2 3
-15%, ZrO 2 0-5%, TiO 2 + ZrO 2 3-15%, B 2 O 3
6~30%, Al 2 O 3 7~20 %, Bi 2 O 3 0~5%, La 2 O 3 0
~5%, Al 2 O 3 + Bi 2 O 3 + La 2 O 3 7~20%, CaO 0~10
%, BaO 0-10%, MgO 0-10%, SrO 0-10%, CaO +
BaO + MgO + SrO 2~13%, Na 2 O + K 2 O + Li 2 O 0~0.7%
A glass bead having a composition consisting of: and wherein the average valence of cation atoms constituting the glass is in the range of 3.41 to 3.65.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63105832A JP2610004B2 (en) | 1988-04-28 | 1988-04-28 | Glass beads |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63105832A JP2610004B2 (en) | 1988-04-28 | 1988-04-28 | Glass beads |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01278434A JPH01278434A (en) | 1989-11-08 |
| JP2610004B2 true JP2610004B2 (en) | 1997-05-14 |
Family
ID=14418021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63105832A Expired - Lifetime JP2610004B2 (en) | 1988-04-28 | 1988-04-28 | Glass beads |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2610004B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7524779B2 (en) | 2003-06-11 | 2009-04-28 | 3M Innovative Properties Company | Microspheres having a high index of refraction |
| US7947616B2 (en) | 2005-11-14 | 2011-05-24 | 3M Innovative Properties Company | Pavement marking, reflective elements, and methods of making microspheres |
| US8591045B2 (en) | 2009-08-21 | 2013-11-26 | 3M Innovative Properties Company | Pavement markings, reflective elements, and methods of making microspheres |
| KR20190044719A (en) * | 2017-10-20 | 2019-05-02 | 공주대학교 산학협력단 | Glass composition with middle refractive index and high hardness for marking road line and glass bead comprising the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53102325A (en) * | 1977-02-18 | 1978-09-06 | Obara Optical Glass | Abrasionn and chemicallproof glass |
| JPS6168349A (en) * | 1984-09-07 | 1986-04-08 | Toshiba Glass Co Ltd | Wear resistant glass bead |
| JPS61270235A (en) * | 1985-05-24 | 1986-11-29 | Ohara Inc | Glass for bead |
| JPS6265953A (en) * | 1985-09-12 | 1987-03-25 | Toshiba Glass Co Ltd | Wear resistant glass beads |
-
1988
- 1988-04-28 JP JP63105832A patent/JP2610004B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7524779B2 (en) | 2003-06-11 | 2009-04-28 | 3M Innovative Properties Company | Microspheres having a high index of refraction |
| US7947616B2 (en) | 2005-11-14 | 2011-05-24 | 3M Innovative Properties Company | Pavement marking, reflective elements, and methods of making microspheres |
| US8591045B2 (en) | 2009-08-21 | 2013-11-26 | 3M Innovative Properties Company | Pavement markings, reflective elements, and methods of making microspheres |
| KR20190044719A (en) * | 2017-10-20 | 2019-05-02 | 공주대학교 산학협력단 | Glass composition with middle refractive index and high hardness for marking road line and glass bead comprising the same |
| KR102005327B1 (en) * | 2017-10-20 | 2019-07-31 | 공주대학교 산학협력단 | Glass composition with middle refractive index and high hardness for marking road line and glass bead comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01278434A (en) | 1989-11-08 |
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