JPH06293533A - Composition for hollow glass sphere and hollow glass sphere produced by using same - Google Patents
Composition for hollow glass sphere and hollow glass sphere produced by using sameInfo
- Publication number
- JPH06293533A JPH06293533A JP10364993A JP10364993A JPH06293533A JP H06293533 A JPH06293533 A JP H06293533A JP 10364993 A JP10364993 A JP 10364993A JP 10364993 A JP10364993 A JP 10364993A JP H06293533 A JPH06293533 A JP H06293533A
- 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 23
- 239000011521 glass Substances 0.000 title abstract description 63
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 claims description 21
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 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 17
- 238000004090 dissolution Methods 0.000 abstract description 3
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum 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
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 15
- 238000010828 elution Methods 0.000 description 8
- 230000005484 gravity Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 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
- 230000000052 comparative effect Effects 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
- 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
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 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
- 238000000034 method Methods 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
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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)
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 ５．０〜１５．０％、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％、ＳＯ3 ０．０５〜
１．５％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 5.0~15.0%, 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 %, SO 3 0.05~
It is characterized by having a composition of 1.5%.
【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
〜１７．０％、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
〜１．７％、Ａｓ2 Ｏ3 ＋Ｓｂ2 Ｏ3 ０〜１．５％、Ｖ
2 Ｏ5 ０〜１０％、ＳＯ3 ０．０５〜１．３％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.
〜17.0%, 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
~ 1.7%, As 2 O 3 + Sb 2 O 3 0-1.5%, V
It is characterized by having a composition of 2 O 5 0 to 10% and SO 3 0.05 to 1.3%.
【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４１．０〜５５．０％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 55.0%. 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.
【００１１】Ａｌ2 Ｏ3 の含有量は５．０〜１５．０
％、好ましくは７．０〜１３．０％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、１
５．０％より多いと溶融性が低下する。The content of Al 2 O 3 is 5.0 to 15.0.
%, Preferably 7.0 to 13.0%. Al 2 O 3
Is less than 5.0%, the durability of the glass deteriorates and 1
If it is more than 5.0%, 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％、好ましくは０〜１．５％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%, preferably 0 to 1.5%.
If the total amount of these components is more than 1.9%, 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 hollow the glass and also have a function of helping the dissolution of 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】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〜
１．５％、好ましくは０．０５〜１．２％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１．５％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 foaming material which hollows out the glass by generating SO 2 gas, and its content is from 0.05 to
It is 1.5%, preferably 0.05 to 1.2%. 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 1.5%.
【００２１】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.
【００２２】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 the mixture is prepared 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.
【００２３】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。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。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. 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 that has a higher viscosity at high temperature than the glass powder. Examples of such a material include an oxide composition (SiO 2 —Al 2 O 3 —CaO) similar to that of hollow glass spheres.
-B 2 O 3) a metal alkoxide that can form a film can be used based solution.
【００２４】このようにして得られ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 ５．０〜１７．０％、Ｂ2 Ｏ3 １．０〜１
５．０％、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 ０〜１．７％、Ａｓ2 Ｏ3 ＋Ｓｂ
2 Ｏ3 ０〜１．５％、Ｖ2Ｏ5 ０〜１０％、ＳＯ3 ０．
０５〜１．３％の組成を有する。The hollow glass spheres of the present invention thus obtained have a weight percentage of SiO 2 of 40.0 to 60.0%,
Al 2 O 3 5.0~17.0%, B 2 O 3 1.0~1
5.0%, CaO 10.0-30.0%, BaO
0.1 to 15.0%, MgO 0 to 10.0%, ZnO
0 to 10.0%, SrO 0 to 10.0%, Na 2 O
+ K 2 O + Li 2 O 0-1.7%, As 2 O 3 + Sb
2 O 3 0 to 1.5%, V 2 O 5 0 to 10%, SO 3 0.
It has a composition of 05 to 1.3%.
【００２５】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 ７．０〜１５．０％、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 ０〜１．５％、Ａｓ2 Ｏ3 ＋Ｓｂ2 Ｏ3 ０〜
１．２％、Ｖ2 Ｏ5 ０〜７％、ＳＯ3 ０．０５〜１．０
％の組成を有するものである。Particularly preferred hollow glass spheres within the above range are SiO 2 42.0 to 58.0% and A by weight percentage.
l 2 O 3 7.0~15.0%, 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 0-1.5%, As 2 O 3 + Sb 2 O 3 0-
1.2%, V 2 O 5 0~7 %, SO 3 0.05~1.0
% Composition.
【００２６】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 depending on 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 ).
【００２７】[0027]
【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.
【００２８】[0028]
【表１】 [Table 1]
【００２９】表１は実施例及び比較例に用いるガラス粉
末（Ｎｏ．１〜１０）を示している。Table 1 shows glass powders (Nos. 1 to 10) used in Examples and Comparative Examples.
【００３０】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.
【００３１】まず、表１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３８μ
ｍ以下のガラス粉末を得た。First, a batch was prepared so as to have the composition shown in Table 1, melted at 1350 ° C. for 2 hours, and then molded. Next, this glass molded body was crushed and classified to 38 μm.
A glass powder of m or less was obtained.
【００３２】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。Subsequently, 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.
【００３３】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.
【００３４】表２は、このようにして作製した実施例
（試料Ｎｏ．１〜７）及び比較例（試料Ｎｏ．８〜１
０）のガラス組成、見掛け比重及びアルカリ溶出量につ
いて示している。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。Table 2 shows examples (Sample Nos. 1 to 7) and comparative examples (Samples No. 8 to 1) thus produced.
The glass composition, apparent specific gravity, and alkali elution amount of 0) are shown. 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.
【００３５】[0035]
【表２】 [Table 2]
【００３６】表２から明らかなように、実施例である試
料Ｎｏ．１〜７は見掛け比重が０．８５〜１．２５ｇ／
ｃｍ3 、アルカリ溶出量が０〜０．８ｍｇとであった。
これに対して比較例である試料Ｎｏ．８〜１０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 Table 2, the sample No. 1 to 7 have an apparent specific gravity of 0.85 to 1.25 g /
cm 3 , and the amount of alkali elution was 0 to 0.8 mg.
On the other hand, sample No. Nos. 8 to 10 had an apparent specific gravity of 0.90 to 1.15 g / cm 3 and showed values equivalent to those of the examples, but the amount of alkali elution was 5 mg or more, which was much higher than that of the examples. .
【００３７】[0037]
【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.
【００３８】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 Ｏ3５．０〜１５．０％、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
％、ＳＯ3 ０．０５〜１．５％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 5.0-15.0%, 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
%, SO 3 0.05 to 1.5% composition for hollow glass spheres.
０．０％、Ａｌ2 Ｏ3５．０〜１７．０％、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 ０〜１．７％、Ａｓ
2 Ｏ3 ＋Ｓｂ2 Ｏ3 ０〜１．５％、Ｖ2 Ｏ5 ０〜１０
％、ＳＯ3 ０．０５〜１．３％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 17.0%, 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 0-1.7%, As
2 O 3 + Sb 2 O 3 0 to 1.5%, V 2 O 5 0 to 10
%, SO 3 0.05-1.3%, hollow glass spheres characterized by the above-mentioned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10364993A JPH06293533A (en) | 1993-04-05 | 1993-04-05 | Composition for hollow glass sphere and hollow glass sphere produced by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10364993A JPH06293533A (en) | 1993-04-05 | 1993-04-05 | Composition for hollow glass sphere and hollow glass sphere produced by using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06293533A true JPH06293533A (en) | 1994-10-21 |
Family
ID=14359630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10364993A Pending JPH06293533A (en) | 1993-04-05 | 1993-04-05 | Composition for hollow glass sphere and hollow glass sphere produced by using same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06293533A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704632B (en) | 2009-11-30 | 2012-08-29 | 中国建材国际工程有限公司 | Preparation method of high-strength low-density hollow glass bead |
| JP2021143089A (en) * | 2020-03-12 | 2021-09-24 | 太平洋セメント株式会社 | Inorganic oxide hollow particles |
| 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 |
| EP4389718A1 (en) * | 2022-12-22 | 2024-06-26 | Cosentino Research & Development, S.L. | Artificial agglomerated stone article comprising granulated vitreous material and method for the manufacture of said article |
| EP4389717A1 (en) * | 2022-12-22 | 2024-06-26 | Cosentino Research & Development, S.L. | Artificial agglomerated stone article comprising opaque white granulated vitreous material and method for the manufacture of said article |
-
1993
- 1993-04-05 JP JP10364993A patent/JPH06293533A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704632B (en) | 2009-11-30 | 2012-08-29 | 中国建材国际工程有限公司 | Preparation method of high-strength low-density hollow glass bead |
| 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 |
| JP2021143089A (en) * | 2020-03-12 | 2021-09-24 | 太平洋セメント株式会社 | Inorganic oxide hollow particles |
| EP4389718A1 (en) * | 2022-12-22 | 2024-06-26 | Cosentino Research & Development, S.L. | Artificial agglomerated stone article comprising granulated vitreous material and method for the manufacture of said article |
| EP4389717A1 (en) * | 2022-12-22 | 2024-06-26 | Cosentino Research & Development, S.L. | Artificial agglomerated stone article comprising opaque white granulated vitreous material and method for the manufacture of said article |
| WO2024133689A1 (en) * | 2022-12-22 | 2024-06-27 | Cosentino Research & Development, S.L. | Artificial agglomerated stone article comprising opaque white granulated vitreous material and method for the manufacture of said article |
| WO2024133623A1 (en) * | 2022-12-22 | 2024-06-27 | Cosentino Research & Development, S.L. | Artificial agglomerated stone article comprising granulated vitreous material and method for the manufacture of said article |
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