JPH0873238A - Composition for hollow glass sphere and hollow glass sphere produced by using this - Google Patents
Composition for hollow glass sphere and hollow glass sphere produced by using thisInfo
- Publication number
- JPH0873238A JPH0873238A JP24060294A JP24060294A JPH0873238A JP H0873238 A JPH0873238 A JP H0873238A JP 24060294 A JP24060294 A JP 24060294A JP 24060294 A JP24060294 A JP 24060294A JP H0873238 A JPH0873238 A JP H0873238A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- hollow glass
- composition
- glass sphere
- hollow
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 239000011521 glass Substances 0.000 title abstract description 66
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 claims description 23
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 6
- 229910052785 arsenic Inorganic materials 0.000 claims description 6
- 239000003513 alkali Substances 0.000 abstract description 16
- 238000010828 elution Methods 0.000 abstract description 9
- 229910018404 Al2 O3 Inorganic materials 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 229910011763 Li2 O Inorganic materials 0.000 abstract 1
- 229910004742 Na2 O Inorganic materials 0.000 abstract 1
- 229910017895 Sb2 O3 Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 21
- 230000005484 gravity Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000006060 molten glass Substances 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
- C03C11/002—Hollow glass particles
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、中空ガラス球用組成物
及びこれを用いて製造した中空ガラス球に関するもので
ある。FIELD OF THE INVENTION The present invention relates to a composition for hollow glass spheres and a hollow glass sphere produced by using the composition.
【０００２】[0002]
【従来の技術】中空ガラス球は軽量で、しかも耐圧強度
が高いという特徴を有しており、従来より各種合成樹脂
の充填材等として使用されている。また軽量であるため
に、ガラス固有の誘電率を大きく低下させることが可能
であり、近年、これらの特徴を生かして中空ガラス球を
プリント配線基板の低誘電率化材として使用することが
提案され、開発が進められている。この用途に用いられ
る中空ガラス球には、低誘電率を達成するために軽量で
あることや、樹脂との接着性が損なわれたり、また基板
の電気絶縁抵抗性が悪化しないように、アルカリイオン
の溶出量が極めて少ないことが要求される。2. Description of the Related Art Hollow glass spheres are lightweight and have high pressure resistance, and have been conventionally used as fillers for various synthetic resins. In addition, because of its light weight, it is possible to greatly reduce the dielectric constant inherent in glass, and in recent years, it has been proposed to use hollow glass spheres as a low dielectric constant material for printed wiring boards by taking advantage of these characteristics. , Is under development. The hollow glass spheres used for this purpose are made of alkali ions so that they are lightweight to achieve a low dielectric constant, their adhesiveness with resins is impaired, and the electrical insulation resistance of the substrate does not deteriorate. Is required to be extremely small.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら従来の中
空ガラス球は、以下の理由からアルカリ成分を多量に含
んでおり、上記要求を満足させるようなアルカリ溶出量
の極めて少ないものが存在しないのが現状である。即
ち、中空ガラス球を製造する方法として、ＳＯ3 を溶融
ガラス中に溶け込ませた後、得られたガラスからガラス
粉末を作製し、これを再溶融することによってガラス中
からＳＯ2 ガスを発生させ、ガラス粉末を内部から膨張
させて中空ガラス球を得る方法が一般的に採用されてい
る。ところが溶融ガラス中のアルカリ成分を少なくする
とＳＯ3 がガラス中に溶け込み難くなるため、再溶融し
てもＳＯ2 ガスが殆ど発生せず、ガラスが中空化しな
い。それゆえガラス中のアルカリ含有量を高くせざるを
得ず、結果としてアルカリ溶出量の極めて少ない中空ガ
ラス球を得ることはできなかった。However, the conventional hollow glass spheres contain a large amount of alkali components for the following reasons, and there is no one with an extremely small amount of alkali elution that satisfies the above requirements. Is. That is, as a method for producing hollow glass spheres, SO 3 is dissolved in molten glass, glass powder is produced from the obtained glass, and SO 2 gas is generated from the glass by remelting it. Generally, a method of expanding glass powder from the inside to obtain a hollow glass sphere is generally adopted. However, when the alkali component in the molten glass is reduced, SO 3 becomes difficult to dissolve in the glass, so SO 2 gas is hardly generated even if re-melted, and the glass does not become hollow. Therefore, the alkali content in the glass had to be increased, and as a result, it was not possible to obtain hollow glass spheres with an extremely small amount of alkali elution.
【０００４】本発明の目的は、アルカリ溶出量が極めて
少ない中空ガラス球を製造することが可能な中空ガラス
球用組成物と、これを用いて製造した中空ガラス球を提
供することである。An object of the present invention is to provide a hollow glass sphere composition capable of producing a hollow glass sphere having an extremely small amount of alkali elution, and a hollow glass sphere produced by using the composition.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、種々の研
究を行った結果、中空ガラス球用組成物において、アル
カリ成分の含有量を１．９％以下に制限するとともに、
一定量以上のＣａＯとＢａＯを含有させることにより上
記目的が達成できることを見いだし、本発明として提案
するものである。As a result of various studies, the inventors of the present invention have limited the content of alkali components to 1.9% or less in the composition for hollow glass spheres, and
It was found that the above object can be achieved by containing a certain amount or more of CaO and BaO, and is proposed as the present invention.
【０００６】即ち、本発明の中空ガラス球用組成物は、
重量百分率で、ＳｉＯ2 ４０．０〜６０．０％、Ａｌ2
Ｏ3 ５．０〜２０．０％、Ｂ2 Ｏ3 ３．０〜２０．０
％、ＣａＯ １０．０〜３０．０％、ＢａＯ ０．１〜
１５．０％、ＭｇＯ ０〜１０．０％、ＺｎＯ ０〜１
０．０％、ＳｒＯ ０〜１０．０％、Ｎａ2 Ｏ＋Ｋ2 Ｏ
＋Ｌｉ2 Ｏ ０〜１．９％、Ａｓ2 Ｏ3 ＋Ｓｂ2 Ｏ3 ０
〜１．５％、Ｖ2 Ｏ5 ０〜１０．０％、ＴｉＯ2 ０〜１
０．０％、ＳＯ3 ０．０５〜３．２％の組成を有するこ
とを特徴とする。That is, the composition for hollow glass spheres of the present invention is
SiO 2 40.0 to 60.0% by weight percentage, Al 2
O 3 5.0~20.0%, B 2 O 3 3.0~20.0
%, CaO 10.0 to 30.0%, BaO 0.1
15.0%, MgO 0-10.0%, ZnO 0-1
0.0%, SrO 0 to 10.0%, Na 2 O + K 2 O
+ Li 2 O 0-1.9%, As 2 O 3 + Sb 2 O 3 0
~1.5%, V 2 O 5 0~10.0 %, TiO 2 0~1
It is characterized by having a composition of 0.0% and SO 3 0.05 to 3.2%.
【０００７】また本発明の中空ガラス球は、重量百分率
で、ＳｉＯ2 ４０．０〜６０．０％、Ａｌ2 Ｏ3 ５．０
〜２２．０％、Ｂ2 Ｏ3 １．０〜１５．０％、ＣａＯ
１０．０〜３０．０％、ＢａＯ ０．１〜１５．０％、
ＭｇＯ ０〜１０．０％、ＺｎＯ ０〜１０．０％、Ｓ
ｒＯ ０〜１０．０％、Ｎａ2 Ｏ＋Ｋ2 Ｏ＋Ｌｉ2 Ｏ０
〜１．９％、Ａｓ2 Ｏ3 ＋Ｓｂ2 Ｏ3 ０〜１．５％、Ｖ
2 Ｏ5 ０〜１０．０％、ＴｉＯ2 ０〜１０．０％、ＳＯ
3 ０．０５〜１．７％の組成を有することを特徴とす
る。Further, the hollow glass sphere of the present invention has a weight percentage of SiO 2 of 40.0 to 60.0% and Al 2 O 3 of 5.0.
~22.0%, B 2 O 3 1.0~15.0 %, CaO
10.0-30.0%, BaO 0.1-15.0%,
MgO 0 to 10.0%, ZnO 0 to 10.0%, S
rO 0 to 10.0%, Na 2 O + K 2 O + Li 2 O0
~ 1.9%, As 2 O 3 + Sb 2 O 3 0-1.5%, V
2 O 5 0~10.0%, TiO 2 0~10.0%, SO
3 0.05 to 1.7% of the composition.
【０００８】[0008]
【作用】本発明の中空ガラス球用組成物は、アルカリ成
分の含有量を制限する代わりにＣａＯとＢａＯを一定量
以上含有させることにより、ガラス中に十分な量のＳＯ
3 を溶存させることができる。In the composition for hollow glass spheres of the present invention, CaO and BaO are contained in a certain amount or more instead of limiting the content of the alkali component, so that a sufficient amount of SO is contained in the glass.
3 can be dissolved.
【０００９】本発明において、中空ガラス球用組成物を
上記のように限定した理由を以下に述べる。In the present invention, the reason why the composition for hollow glass spheres is limited as described above will be described below.
【００１０】ＳｉＯ2 の含有量は４０．０〜６０．０
％、好ましくは４１．０〜５８．０％である。ＳｉＯ2
が４０．０％より少ないとガラスの耐久性が悪化し、６
０．０％より多いとガラス溶融時のＳＯ3 溶存量が低下
するため、ガラスの再溶融時にＳＯ2 ガスの発生量が少
なくなって中空化し難くなる。The content of SiO 2 is 40.0 to 60.0
%, Preferably 41.0 to 58.0%. SiO 2
Is less than 40.0%, the durability of the glass deteriorates, and 6
When it is more than 0.0%, the dissolved amount of SO 3 at the time of melting the glass decreases, so that the amount of SO 2 gas generated at the time of remelting the glass becomes small and it becomes difficult to hollow the glass.
【００１１】Ａｌ2 Ｏ3 の含有量は５．０〜２０．０
％、好ましくは５．０〜１８．０％である。Ａｌ2 Ｏ3
が５．０％より少ないとガラスの耐久性が悪化し、２
０．０％より多いと溶融性が低下する。The content of Al 2 O 3 is 5.0 to 20.0.
%, Preferably 5.0 to 18.0%. Al 2 O 3
Is less than 5.0%, the durability of the glass deteriorates and 2
If it is more than 0.0%, the meltability will decrease.
【００１２】Ｂ2 Ｏ3 の含有量は３．０〜２０．０％、
好ましくは５．０〜１５．０％である。Ｂ2 Ｏ3 が３．
０％より少ないとガラスの溶融性が低下し、２０．０％
より多いと中空ガラス球の耐圧強度が低下し、またＳＯ
3 の溶存量が低下する。The content of B 2 O 3 is 3.0 to 20.0%,
It is preferably 5.0 to 15.0%. B 2 O 3 is 3.
If it is less than 0%, the meltability of the glass decreases, and 20.0%
If it is more, the compressive strength of the hollow glass sphere will decrease, and the SO
Dissolved amount of 3 decreases.
【００１３】ＣａＯはガラスの溶融性を向上させ、且
つ、ＳＯ3 をガラス中に溶存させるための成分であり、
その含有量は１０．０〜３０．０％、好ましくは１８．
０〜２５．０％である。ＣａＯが１０．０％より少ない
とＳＯ3 の溶存量が著しく低下する結果、再溶融時にＳ
Ｏ2 ガスが発生せず、中空化が困難になる。一方、３
０．０％より多いとガラスが失透し好ましくない。CaO is a component for improving the meltability of glass and for dissolving SO 3 in the glass.
Its content is 10.0 to 30.0%, preferably 18.
It is 0 to 25.0%. If the content of CaO is less than 10.0%, the dissolved amount of SO 3 will remarkably decrease.
O 2 gas is not generated and hollowing becomes difficult. On the other hand, 3
If it exceeds 0.0%, the glass is devitrified, which is not preferable.
【００１４】ＢａＯもガラスの溶融性を向上させ、且
つ、ＳＯ3 をガラス中に溶存させるための成分であり、
その含有量は０．１〜１５．０％、好ましくは０．１〜
１３．０％である。ＢａＯが０．１％より少ないとＳＯ
3 の溶存量が著しく低下する。一方、１５．０％より多
いとガラスが失透し好ましくない。BaO is also a component for improving the meltability of glass and for dissolving SO 3 in the glass.
Its content is 0.1 to 15.0%, preferably 0.1 to
It is 13.0%. If BaO is less than 0.1%, SO
The dissolved amount of 3 is significantly reduced. On the other hand, if it exceeds 15.0%, the glass is devitrified, which is not preferable.
【００１５】ＭｇＯ、ＺｎＯ及びＳｒＯは、ＣａＯやＢ
ａＯと同様溶融性を向上させるとともに、ＳＯ3 の溶存
に寄与する成分であり、これらの成分の含有量は何れも
０〜１０．０％、好ましくは０〜６．０％である。これ
らの成分が多すぎるとガラスが失透し易くなる。MgO, ZnO and SrO are CaO and B
Like aO, it is a component that improves the meltability and contributes to the dissolution of SO 3 , and the content of each of these components is 0 to 10.0%, preferably 0 to 6.0%. If these components are too much, the glass tends to devitrify.
【００１６】なおＣａＯ、ＢａＯ、ＭｇＯ、ＺｎＯ及び
ＳｒＯの合量は１５．０〜４０．０％であることが好ま
しく、特に２０．０〜３５．０％であることが望まし
い。The total content of CaO, BaO, MgO, ZnO and SrO is preferably 15.0 to 40.0%, more preferably 20.0 to 35.0%.
【００１７】Ｎａ2 Ｏ、Ｋ2 Ｏ及びＬｉ2 Ｏの含有量は
合量で０〜１．９％である。これらの成分の合量が１．
９％より多いと、合成樹脂に充填したときにアルカリイ
オンが多量に溶出してしまう。The total content of Na 2 O, K 2 O and Li 2 O is 0 to 1.9%. The total amount of these components is 1.
If it is more than 9%, a large amount of alkali ions will be eluted when the synthetic resin is filled.
【００１８】Ａｓ2 Ｏ3 とＳｂ2 Ｏ3 はガラスの再溶融
時にＯ2 ガスを発生させてガラスを中空化させる発泡材
であるとともに、溶融ガラス中へのＳＯ3 の溶解を助け
る働きがあり、これら成分の含有量は合量で０〜１．５
％、好ましくは０〜１．２％である。これらの成分の合
量が１．５％より多いとガラス溶融時に異物を発生させ
てしまい好ましくない。As 2 O 3 and Sb 2 O 3 are foaming materials that generate O 2 gas when the glass is remelted to make the glass hollow, and also have a function of helping to dissolve SO 3 in the molten glass. , The total content of these components is 0-1.5
%, Preferably 0 to 1.2%. If the total content of these components is more than 1.5%, foreign matters are generated when the glass is melted, which is not preferable.
【００１９】Ｖ2 Ｏ5 は再溶融時にガラスの表面張力を
低下させて中空化の助剤となるものであり、その含有量
は０〜１０．０％、好ましくは０〜７．０％である。Ｖ
2 Ｏ5 が１０．０％より多いとガラスへの着色効果が大
きくなり過ぎる。V 2 O 5 serves as an auxiliary agent for hollowing by lowering the surface tension of the glass at the time of remelting, and its content is 0 to 10.0%, preferably 0 to 7.0%. is there. V
If 2 O 5 is more than 10.0%, the coloring effect on the glass becomes too large.
【００２０】ＴｉＯ2 は化学耐久性を向上させる成分で
あり、その含有量は０〜１０．０％、好ましくは０〜
７．０％である。ＴｉＯ2 が１０．０％より多くなると
再溶融時の発泡性が悪くなる。TiO 2 is a component for improving chemical durability, and its content is 0 to 10.0%, preferably 0 to
7.0%. When the content of TiO 2 is more than 10.0%, the foaming property at the time of remelting becomes poor.
【００２１】ＳＯ3 はＳＯ2 ガスを発生させてガラスを
中空化させる発泡材であり、その含有量は０．０５〜
３．２％、好ましくは０．０５〜２．６％である。ＳＯ
3 が０．０５％より少ないとＳＯ2 ガスの発生が不十分
になって中空ガラス球を作ることができない。一方、Ｓ
Ｏ3 は３．２％より多量にはガラス中に溶存することが
できない。SO 3 is a foam material that hollows out the glass by generating SO 2 gas, and its content is from 0.05 to
It is 3.2%, preferably 0.05 to 2.6%. SO
If the content of 3 is less than 0.05%, the generation of SO 2 gas is insufficient and hollow glass spheres cannot be produced. On the other hand, S
O 3 cannot dissolve in the glass in an amount greater than 3.2%.
【００２２】次に、上記中空ガラス球用組成物を用いて
本発明の中空ガラス球を製造する方法について述べる。Next, a method for producing the hollow glass sphere of the present invention using the above composition for hollow glass sphere will be described.
【００２３】まず、ガラス原料及び発泡材を上記した組
成範囲となるように調合し、これを１２５０〜１４００
℃で１〜４時間溶融した後、成形し、粉砕、分級するこ
とによってガラス粉末を作製する。なおガラス粉末の粒
径は３８μｍ以下にすることが好ましい。First, the glass raw material and the foaming material are blended so as to have the above-mentioned composition range, and these are blended from 1250 to 1400.
After melting at 1 ° C. for 1 to 4 hours, glass powder is produced by molding, crushing and classifying. The particle size of the glass powder is preferably 38 μm or less.
【００２４】次に作製したガラス粉末を１５００〜１７
００℃の火炎中を通過させて再溶融することによって、
ガラス中からＳＯ2 ガスを発生させ、ガラス粉末を内部
から膨張させて中空ガラス球を得る。Next, the glass powder prepared was used for 1500 to 17
By passing through a flame of 00 ° C and remelting,
SO 2 gas is generated from the glass, and the glass powder is expanded from the inside to obtain hollow glass spheres.
【００２５】なお、再溶融時に発生したガスがガラス球
表面から発散し易い場合、予めガラス粉末表面に、高温
における粘性がガラス粉末よりも高粘性となる被膜材料
をコーティングしておくことが望ましい。このような材
料としては、例えば中空ガラス球と同様の酸化物組成
（ＳｉＯ2 −Ａｌ2 Ｏ3 −ＣａＯ−Ｂ2 Ｏ3 ）被膜を形
成し得る金属アルコキシドを主成分とする溶液を使用す
ることができる。またこのような方法以外にも、作製し
たガラス粉末を発泡性粉末（例えばＣａＳＯ4 ・２Ｈ2
Ｏ等）と混合し、発泡性粉末が発泡しない程度の温度で
焼結させ、次いでこれを粉砕して複合粉末とした後、こ
れを火炎中に供給することにより、中空ガラス球を得る
ことができる。When the gas generated at the time of remelting is likely to diffuse from the surface of the glass sphere, it is desirable to previously coat the surface of the glass powder with a coating material having a viscosity higher than that of the glass powder at a high temperature. As such a material, for example, a solution containing a metal alkoxide as a main component capable of forming a film having the same oxide composition (SiO 2 —Al 2 O 3 —CaO—B 2 O 3 ) as a hollow glass sphere should be used. You can In addition to this method, the produced glass powder may be used as a foamable powder (for example, CaSO 4 .2H 2
O, etc.) and sintered at a temperature at which the expandable powder does not foam, and then crushed into a composite powder, which is then fed into a flame to obtain hollow glass spheres. it can.
【００２６】このようにして得られる中空ガラス球は、
中空化のための再溶融によりＢ2 Ｏ3 、ＳＯ3 等の揮発
し易い成分が減少し、ＳｉＯ2 、Ａｌ2 Ｏ3 等の成分が
相対的に増加するため、上記したガラス粉末とは若干組
成が変化する。本発明においては、得られる中空ガラス
球は重量百分率でＳｉＯ2 ４０．０〜６０．０％、Ａｌ
2 Ｏ3 ５．０〜２２．０％、Ｂ2 Ｏ3 １．０〜１５．０
％、ＣａＯ １０．０〜３０．０％、ＢａＯ ０．１〜
１５．０％、ＭｇＯ ０〜１０．０％、ＺｎＯ０〜１
０．０％、ＳｒＯ ０〜１０．０％、Ｎａ2 Ｏ＋Ｋ2 Ｏ
＋Ｌｉ2 Ｏ ０〜１．９％、Ａｓ2 Ｏ3 ＋Ｓｂ2 Ｏ3 ０
〜１．５％、Ｖ2Ｏ5 ０〜１０．０％、ＴｉＯ2 ０〜１
０．０％、ＳＯ3 ０．０５〜１．７％の組成を有する。The hollow glass spheres thus obtained are
Due to remelting for hollowing, components such as B 2 O 3 and SO 3 which are easily volatilized are reduced, and components such as SiO 2 and Al 2 O 3 are relatively increased. The composition changes. In the present invention, the hollow glass spheres obtained have a weight percentage of SiO 2 40.0 to 60.0% and Al.
2 O 3 5.0 to 22.0%, B 2 O 3 1.0 to 15.0
%, CaO 10.0 to 30.0%, BaO 0.1
15.0%, MgO 0-10.0%, ZnO 0-1
0.0%, SrO 0 to 10.0%, Na 2 O + K 2 O
+ Li 2 O 0-1.9%, As 2 O 3 + Sb 2 O 3 0
~1.5%, V 2 O 5 0~10.0 %, TiO 2 0~1
It has a composition of 0.0% and SO 3 0.05 to 1.7%.
【００２７】上記範囲の中でも特に好ましい中空ガラス
球は、重量百分率でＳｉＯ2 ４２．０〜５８．０％、Ａ
ｌ2 Ｏ3 ５．０〜２０．０％、Ｂ2 Ｏ3 ２．０〜１２．
０％、ＣａＯ １８．０〜２７．０％、ＢａＯ ０．１
〜１３．０％、ＭｇＯ ０〜６．０％、ＺｎＯ ０〜
６．０％、ＳｒＯ ０〜６．０％、Ｎａ2 Ｏ＋Ｋ2 Ｏ＋
Ｌｉ2 Ｏ ０〜１．９％、Ａｓ2 Ｏ3 ＋Ｓｂ2 Ｏ3 ０〜
１．２％、Ｖ2 Ｏ5 ０〜７．０％、ＴｉＯ2 ０〜７．０
％、ＳＯ3 ０．０５〜１．５％の組成を有するものであ
る。Particularly preferable hollow glass spheres within the above range are SiO 2 42.0 to 58.0% by weight percentage, A
l 2 O 3 5.0~20.0%, B 2 O 3 2.0~12.
0%, CaO 18.0 to 27.0%, BaO 0.1
~ 13.0%, MgO 0-6.0%, ZnO 0-
6.0%, SrO 0-6.0%, Na 2 O + K 2 O +
Li 2 O 0-1.9%, As 2 O 3 + Sb 2 O 3 0-
1.2%, V 2 O 5 0~7.0 %, TiO 2 0~7.0
%, SO 3 0.05 to 1.5%.
【００２８】なお本発明の中空ガラス球は、用途に応じ
て見掛け比重を適宜調整することができる。例えばプリ
ント配線基板の充填材として用いる場合、作業性の点か
ら使用する合成樹脂の比重（約１．０〜１．３ｇ／ｃｍ
3 程度）とほぼ同等の０．９〜１．４ｇ／ｃｍ3 の見掛
け比重になるようにすることが望ましい。The apparent specific gravity of the hollow glass sphere of the present invention can be appropriately adjusted according to the application. For example, when used as a filler for a printed wiring board, the specific gravity of the synthetic resin used (about 1.0 to 1.3 g / cm) from the viewpoint of workability.
It is desirable to have an apparent specific gravity of 0.9 to 1.4 g / cm 3 , which is almost the same as (about 3 ).
【００２９】[0029]
【実施例】以下、本発明を実施例に基づいて説明する。EXAMPLES The present invention will be described below based on examples.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【表２】 [Table 2]
【００３２】表１は実施例に用いるガラス粉末（試料Ｎ
ｏ．１〜１０）を、表２は比較例に用いるガラス粉末
（試料Ｎｏ．１１〜１３）をそれぞれ示している。Table 1 shows the glass powder used in the examples (Sample N).
o. 1 to 10) and Table 2 shows glass powders (Sample Nos. 11 to 13) used in Comparative Examples.
【００３３】表の各ガラス粉末は次のようにして調製し
た。Each glass powder in the table was prepared as follows.
【００３４】まず、表の組成になるようにバッチを調合
し、これを１３５０℃で２時間溶融した後、成形した。
次いでこのガラス成形体を粉砕し、分級して３８μｍ以
下のガラス粉末を得た。First, a batch was prepared so as to have the composition shown in the table, which was melted at 1350 ° C. for 2 hours and then molded.
Next, this glass molded body was crushed and classified to obtain glass powder of 38 μm or less.
【００３５】続いて得られたガラス粉末と、金属アルコ
キシド（金属としてＳｉ、Ｂ）、可溶性無機塩（Ａｌ
（ＮＯ3 ）3 ・９Ｈ2 ＯとＣａ（ＮＯ3 ）2 ・４Ｈ2
Ｏ）、水及びイソプロピルアルコールからなるコーティ
ング液とを混合してスラリー状にし、ディスパーコート
（日清エンジニアリング株式会社製）にて加熱すること
により、ガラス粉末表面に、ＳｉＯ2 −Ａｌ2 Ｏ3 −Ｃ
ａＯ−Ｂ2 Ｏ3 膜をコーティングした。Then, the obtained glass powder, metal alkoxide (Si and B as metals), soluble inorganic salt (Al
(NO 3) 3 · 9H 2 O and Ca (NO 3) 2 · 4H 2
O), water and a coating liquid consisting of isopropyl alcohol to form a slurry, and heating with a disper coat (manufactured by Nisshin Engineering Co., Ltd.) causes SiO 2 —Al 2 O 3 — on the glass powder surface. C
It was coated aO-B 2 O 3 film.
【００３６】さらにこのガラス粉末を、１６００℃を最
高温度とする火炎中に５〜１００ミリ秒間通過させて再
溶融することにより、ガラス中からＳＯ2 ガスやＯ2 ガ
スを発生させ、これによってガラス粉末を内部から膨張
させて、粒径４５μｍ以下の中空ガラス球を作製した。Further, this glass powder is passed through a flame having a maximum temperature of 1600 ° C. for 5 to 100 milliseconds to be remelted to generate SO 2 gas or O 2 gas, and thereby the glass is generated. The powder was expanded from the inside to produce hollow glass spheres having a particle size of 45 μm or less.
【００３７】表３及び表４は、表１及び表２のガラス粉
末を用いて作製した実施例（試料Ｎｏ．１〜１０）及び
比較例（試料Ｎｏ．１１〜１３）の中空ガラス球の組
成、見掛け比重及びアルカリ溶出量を示すものである。
なお見掛け比重はウルトラピクノメーター（クアンタク
ロム株式会社製）を用いて測定し、またアルカリ溶出量
はＪＩＳ Ｒ１６０２に準拠して測定した。Tables 3 and 4 show the compositions of the hollow glass spheres of Examples (Sample Nos. 1 to 10) and Comparative Examples (Samples No. 11 to 13) produced by using the glass powders of Tables 1 and 2. , And apparent specific gravity and alkali elution amount.
The apparent specific gravity was measured using an ultra pycnometer (manufactured by Quantachrome Co., Ltd.), and the alkali elution amount was measured in accordance with JIS R1602.
【００３８】[0038]
【表３】 [Table 3]
【００３９】[0039]
【表４】 [Table 4]
【００４０】表３及び表４から明らかなように、実施例
である試料Ｎｏ．１〜１０は見掛け比重が０．６６〜
１．２５ｇ／ｃｍ3 、アルカリ溶出量が０〜０．８ｍｇ
であった。これに対して比較例である試料Ｎｏ．１１〜
１３は、見掛け比重が０．９０〜１．１５ｇ／ｃｍ3 で
あり、実施例と同等の値を示したものの、アルカリ溶出
量が５ｍｇ以上であり、実施例に比べて非常に多かっ
た。As is clear from Tables 3 and 4, the sample No. 1 to 10 have an apparent specific gravity of 0.66
1.25 g / cm 3 , alkaline elution amount of 0 to 0.8 mg
Met. On the other hand, sample No. which is a comparative example. 11-
Sample No. 13 had an apparent specific gravity of 0.90 to 1.15 g / cm 3 and showed a value equivalent to that of the example, but the amount of alkali elution was 5 mg or more, which was much larger than that of the example.
【００４１】[0041]
【発明の効果】本発明の中空ガラス球用組成物は、アル
カリ成分を多量含んでいなくても、十分な量のＳＯ3 を
ガラス中に溶存しておくことが可能なため、アルカリ含
有量の少ない中空ガラス球を製造することが可能であ
る。INDUSTRIAL APPLICABILITY The composition for hollow glass spheres of the present invention can dissolve a sufficient amount of SO 3 in glass even if it does not contain a large amount of alkali component. It is possible to manufacture hollow glass spheres with a small amount.
【００４２】また本発明の中空ガラス球は、軽量で、且
つ、耐圧強度が高い。しかもアルカリ溶出量が極めて少
ないために、各種樹脂の充填材、特にプリント配線基板
の充填材として好適である。The hollow glass sphere of the present invention is lightweight and has high pressure resistance. In addition, since the amount of alkali elution is extremely small, it is suitable as a filler for various resins, particularly as a filler for printed wiring boards.
Claims (2)
０．０％、Ａｌ2 Ｏ3５．０〜２０．０％、Ｂ2 Ｏ3
３．０〜２０．０％、ＣａＯ １０．０〜３０．０％、
ＢａＯ ０．１〜１５．０％、ＭｇＯ ０〜１０．０
％、ＺｎＯ ０〜１０．０％、ＳｒＯ ０〜１０．０
％、Ｎａ2 Ｏ＋Ｋ2 Ｏ＋Ｌｉ2 Ｏ ０〜１．９％、Ａｓ
2 Ｏ3 ＋Ｓｂ2 Ｏ3 ０〜１．５％、Ｖ2 Ｏ5 ０〜１０．
０％、ＴｉＯ2０〜１０．０％、ＳＯ3 ０．０５〜３．
２％の組成を有することを特徴とする中空ガラス球用組
成物。1. SiO 2 40.0-6 by weight percentage.
0.0%, Al 2 O 3 5.0 to 20.0%, B 2 O 3
3.0-20.0%, CaO 10.0-30.0%,
BaO 0.1-15.0%, MgO 0-10.0
%, ZnO 0 to 10.0%, SrO 0 to 10.0
%, Na 2 O + K 2 O + Li 2 O 0-1.9%, As
2 O 3 + Sb 2 O 3 0 to 1.5%, V 2 O 5 0 to 10.
0%, TiO 2 0 to 10.0%, SO 3 0.05 to 3.
A composition for hollow glass spheres having a composition of 2%.
０．０％、Ａｌ2 Ｏ3５．０〜２２．０％、Ｂ2 Ｏ3
１．０〜１５．０％、ＣａＯ １０．０〜３０．０％、
ＢａＯ ０．１〜１５．０％、ＭｇＯ ０〜１０．０
％、ＺｎＯ ０〜１０．０％、ＳｒＯ ０〜１０．０
％、Ｎａ2 Ｏ＋Ｋ2 Ｏ＋Ｌｉ2 Ｏ ０〜１．９％、Ａｓ
2 Ｏ3 ＋Ｓｂ2 Ｏ3 ０〜１．５％、Ｖ2 Ｏ5 ０〜１０．
０％、ＴｉＯ2０〜１０．０％、ＳＯ3 ０．０５〜１．
７％の組成を有することを特徴とする中空ガラス球。2. SiO 2 40.0-6 by weight percentage.
0.0%, Al 2 O 3 5.0 to 22.0%, B 2 O 3
1.0-15.0%, CaO 10.0-30.0%,
BaO 0.1-15.0%, MgO 0-10.0
%, ZnO 0 to 10.0%, SrO 0 to 10.0
%, Na 2 O + K 2 O + Li 2 O 0-1.9%, As
2 O 3 + Sb 2 O 3 0 to 1.5%, V 2 O 5 0 to 10.
0%, TiO 2 0~10.0%, SO 3 0.05~1.
Hollow glass spheres having a composition of 7%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24060294A JPH0873238A (en) | 1994-09-07 | 1994-09-07 | Composition for hollow glass sphere and hollow glass sphere produced by using this |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24060294A JPH0873238A (en) | 1994-09-07 | 1994-09-07 | Composition for hollow glass sphere and hollow glass sphere produced by using this |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0873238A true JPH0873238A (en) | 1996-03-19 |
Family
ID=17061939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24060294A Pending JPH0873238A (en) | 1994-09-07 | 1994-09-07 | Composition for hollow glass sphere and hollow glass sphere produced by using this |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0873238A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1160212A1 (en) * | 2000-05-31 | 2001-12-05 | Asahi Glass Co., Ltd. | Hollow glass microspheres and method for producing the same |
| CN102320743A (en) * | 2011-09-29 | 2012-01-18 | 蚌埠玻璃工业设计研究院 | Aluminosilicate HS hollow glass micropearl and preparation method thereof |
| EP4082979A4 (en) * | 2019-12-27 | 2023-01-18 | Nichias Corporation | INORGANIC FIBERS, INORGANIC FIBER PRODUCT, METHOD FOR MAKING AN INORGANIC FIBER PRODUCT, COMPOSITION FOR MAKING AN INORGANIC FIBER, AND METHOD FOR MAKING AN INORGANIC FIBER |
| JP2024014316A (en) * | 2022-07-22 | 2024-02-01 | 太平洋セメント株式会社 | Inorganic oxide hollow particles |
| EP4299541A4 (en) * | 2021-06-29 | 2025-04-09 | Nitto Boseki Co., Ltd. | GLASS COMPOSITION FOR GLASS FIBERS, GLASS FIBER AND GLASS FIBER REINFORCED RESIN MOLDED ARTICLES |
-
1994
- 1994-09-07 JP JP24060294A patent/JPH0873238A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1160212A1 (en) * | 2000-05-31 | 2001-12-05 | Asahi Glass Co., Ltd. | Hollow glass microspheres and method for producing the same |
| CN102320743A (en) * | 2011-09-29 | 2012-01-18 | 蚌埠玻璃工业设计研究院 | Aluminosilicate HS hollow glass micropearl and preparation method thereof |
| EP4082979A4 (en) * | 2019-12-27 | 2023-01-18 | Nichias Corporation | INORGANIC FIBERS, INORGANIC FIBER PRODUCT, METHOD FOR MAKING AN INORGANIC FIBER PRODUCT, COMPOSITION FOR MAKING AN INORGANIC FIBER, AND METHOD FOR MAKING AN INORGANIC FIBER |
| EP4299541A4 (en) * | 2021-06-29 | 2025-04-09 | Nitto Boseki Co., Ltd. | GLASS COMPOSITION FOR GLASS FIBERS, GLASS FIBER AND GLASS FIBER REINFORCED RESIN MOLDED ARTICLES |
| JP2024014316A (en) * | 2022-07-22 | 2024-02-01 | 太平洋セメント株式会社 | Inorganic oxide hollow particles |
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