JPH09263732A - Inorganic adhesive composition - Google Patents
Inorganic adhesive compositionInfo
- Publication number
- JPH09263732A JPH09263732A JP7439296A JP7439296A JPH09263732A JP H09263732 A JPH09263732 A JP H09263732A JP 7439296 A JP7439296 A JP 7439296A JP 7439296 A JP7439296 A JP 7439296A JP H09263732 A JPH09263732 A JP H09263732A
- Authority
- JP
- Japan
- Prior art keywords
- composition
- water
- colloidal silica
- particle size
- adhesive composition
- 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.)
- Granted
Links
Landscapes
- Joining Of Glass To Other Materials (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、無機質接着剤組成
物に関する。さらに詳細には、安定化したコロイダルシ
リカをバインダとして用いる安定性に優れた無機質接着
剤組成物に関する。TECHNICAL FIELD The present invention relates to an inorganic adhesive composition. More specifically, it relates to an inorganic adhesive composition having excellent stability, which uses stabilized colloidal silica as a binder.
【０００２】[0002]
【従来の技術】無機質接着剤は、一般に水ガラス、珪酸
リチウム、コロイダルシリカ、燐酸アルミニウム等のバ
インダに酸化物をフィラーとして混合することにより調
製される。2. Description of the Related Art Inorganic adhesives are generally prepared by mixing a binder such as water glass, lithium silicate, colloidal silica or aluminum phosphate with an oxide as a filler.
【０００３】ランプを構成するガラス材料と金属、セラ
ミックス等から成る口金材料とを無機質接着剤で固着す
ることはすでに報告されている。たとえば、特公昭５５
−１４８２０は、コロイダルシリカをバインダとし、耐
火物粉末をフィラーとして混合したランプ用無機質接着
剤を開示する。It has already been reported that the glass material constituting the lamp and the base material made of metal, ceramics or the like are fixed by an inorganic adhesive. For example, Japanese Patent Publication Sho 55
No.-14820 discloses an inorganic adhesive for a lamp in which colloidal silica is used as a binder and refractory powder is mixed as a filler.
【０００４】しかしながら、コロイダルシリカは、水ガ
ラス、珪酸リチウム、燐酸アルミニウムと比較してゲル
化を起こしやすく、特に酸化物（耐火物）と混合して、
無機質接着剤を調製するとき、このゲル化が加速され問
題となっていた。特に、自動充填性、フィラーの沈降性
の２点より、耐火物を微粒化したフィラーを使用した場
合、無機質接着剤が増粘、固化し、１週間〜１ケ月以内
で使用不能となることが頻繁であった。このため、接着
剤を大量に製造し貯蔵することが難しく、受注があって
から製造するのが慣行であった。さらに、製品の輸送も
保冷庫で運ぶ等の特殊な移送方法が必要であり、使用者
側でも製品を使用するまで５〜１０℃の保冷庫に保管す
るなどして、取扱いが煩雑でコストも高くなっている。However, colloidal silica is more likely to cause gelation than water glass, lithium silicate and aluminum phosphate, and especially when mixed with an oxide (refractory),
This gelation has been a problem when the inorganic adhesive is prepared, which is accelerated. In particular, from the two viewpoints of automatic filling property and sedimentation property of the filler, when a filler in which refractory material is atomized is used, the inorganic adhesive may thicken and solidify, and become unusable within 1 week to 1 month. It was frequent. For this reason, it is difficult to manufacture and store a large amount of adhesive, and it is customary to manufacture it after receiving an order. In addition, the product must be transported in a cool box or other special transportation method, and the user must store the product in a cool box at 5 to 10 ° C until it is used. It's getting higher.
【０００５】[0005]
【発明が解決しようとする課題】コロイダルシリカを安
定化する方法は、種々提案されてきたが、それらの方法
を接着剤に適用しても期待する安定性が得られない。こ
れは、接着剤組成物中に存在するフィラーが安定化に干
渉し悪影響を及ぼすためである。したがって、コロイダ
ルシリカのみを公知の方法で安定化してもそれをフィラ
ーとともに使用する接着剤組成物においてその安定化効
果は組成物の安定化に結び付かない。Various methods for stabilizing colloidal silica have been proposed, but even if these methods are applied to an adhesive, the expected stability cannot be obtained. This is because the filler present in the adhesive composition interferes with the stabilization and adversely affects it. Therefore, even if only colloidal silica is stabilized by a known method, its stabilizing effect does not lead to stabilization of the composition in an adhesive composition using it together with a filler.
【０００６】本発明の目的は、上記の問題を解決するた
め、コロイダルシリカをバインダとし、粉末状酸化物を
フィラーとして成る安定化された無機質接着剤組成物を
提供することである。In order to solve the above problems, it is an object of the present invention to provide a stabilized inorganic adhesive composition comprising colloidal silica as a binder and powdery oxide as a filler.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、所定粒子
径のコロイダルシリカと所定粒子径の粉末状酸化物フィ
ラーとから成る接着剤組成物において、５０℃で３日以
上前記組成物を保持後、組成物中の水溶性Ｎａ2Ｏの濃
度およびｐＨ値が所定範囲内であればコロイダルシリカ
のゲル化が抑制され、増粘、固化を示さないことを見出
し、本発明の組成物を完成した。さらに、水溶性Ｎａ2
Ｏの濃度を所定範囲に保つため、予め水溶性Ｎａ2Ｏあ
るいはその前駆体をバインダであるコロイダルシリカ
に、またはフィラーに添加することが有効であることを
見出した。Means for Solving the Problems The present inventors have prepared an adhesive composition comprising colloidal silica having a predetermined particle size and a powdered oxide filler having a predetermined particle size at 50 ° C. for 3 days or more. After the holding, it was found that if the concentration and pH value of the water-soluble Na 2 O in the composition are within a predetermined range, gelation of colloidal silica is suppressed, and the composition does not thicken or solidify. completed. In addition, water-soluble Na 2
It has been found that it is effective to preliminarily add water-soluble Na 2 O or its precursor to colloidal silica as a binder or to a filler in order to keep the concentration of O within a predetermined range.
【０００８】すなわち、本発明は、粒子径５〜３００ｍ
μのコロイダルシリカを主成分とするバインダを固形分
換算で６〜２０重量％と、平均粒子径１〜３０μの粉末
状酸化物を固形分換算で５０〜９０重量％と、残部とし
て水とを含んで成る組成物であり、かつ該組成物を５０
℃で３日以上保持した後、組成物中の水溶性Ｎａ2Ｏの
濃度が３００〜１，５００ｐｐｍであり、そして組成物
のｐＨが９．５〜１１．０の範囲にあることを特徴とす
る無機質接着剤組成物を提供する。さらに本発明は、粒
子径５〜３００ｍμのコロイダルシリカを主成分とする
バインダを固形分換算で６〜２０重量％と、平均粒子径
１〜３０μの粉末状酸化アルミニウムを固形分換算で３
０〜９０重量％と、平均粒子径１〜３０μの付加的粉末
状酸化物を固形分換算で０〜７０重量％と、残部として
水とを含んで成る組成物であり、かつ該組成物を５０℃
で３日以上保持した後、組成物中の水溶性Ｎａ2Ｏの濃
度が３００〜１，５００ｐｐｍであり、そして組成物の
ｐＨが９．５〜１１．０の範囲にあることを特徴とする
無機質接着剤組成物を提供する。ここで「付加的粉末状
酸化物」とは、酸化アルミニウム以外の酸化物の粉末を
指す。前記無機質接着剤組成物では、粉末状酸化アルミ
ニウムは、Ｎａ2Ｏを０．１〜０．８重量％含有するこ
とが好ましい。加えて本発明は、粒子径５〜３００ｍμ
のコロイダルシリカを主成分とするバインダを固形分換
算で６〜２０重量％と、平均粒子径１〜３０μの粉末状
ムライトを固形分換算で３０〜９０重量％と、平均粒子
径１〜３０μの付加的粉末状酸化物を固形分換算で０〜
７０重量％と、残部として水とを含んで成る組成物であ
り、かつ該組成物を５０℃で３日以上保持した後、組成
物中の水溶性Ｎａ2Ｏの濃度が３００〜１，５００ｐｐ
ｍであり、さらに水溶性Ｎａ2Ｏの濃度がムライト当た
りに換算すると４００ｐｐｍ以上であり、そして組成物
のｐＨが９．５〜１１．０の範囲にあることを特徴とす
る無機質接着剤組成物を提供する。ここで「付加的粉末
状酸化物」とは、ムライト以外の酸化物の粉末を指す。
前記無機質接着剤組成物において、バインダは、コロイ
ダルシリカに水溶性Ｎａ2Ｏを添加したものであること
が好ましい。本発明に用いるコロイダルシリカとして
は、粒子径１０〜２０ｍμのものが好ましく、特に粒子
径１５〜２０ｍμのものがさらに好ましい。本発明に用
いる粉末状酸化物としては、平均粒子径１〜１０μのも
のが好ましい。That is, the present invention has a particle size of 5 to 300 m.
6 to 20% by weight of a binder containing μ colloidal silica as a main component in terms of solid content, 50 to 90% by weight of a powdery oxide having an average particle diameter of 1 to 30 μ in terms of solid content, and water as the balance. A composition comprising: and 50
The composition is characterized by having a concentration of water-soluble Na 2 O in the composition of 300 to 1,500 ppm and keeping the pH of the composition in the range of 9.5 to 11.0 after holding at 3 ° C. for 3 days or more. An inorganic adhesive composition is provided. Further, according to the present invention, a binder containing a colloidal silica as a main component having a particle diameter of 5 to 300 m6 in a solid content of 6 to 20% by weight and a powdery aluminum oxide having an average particle diameter of 1 to 30 µ in a solid content of 3 are used.
A composition comprising 0 to 90% by weight, 0 to 70% by weight of an additional powdery oxide having an average particle diameter of 1 to 30 μm in terms of solid content, and water as the balance. 50 ° C
The composition is characterized by having a concentration of water-soluble Na 2 O in the composition of 300 to 1,500 ppm and holding the pH of the composition in the range of 9.5 to 11.0 after holding for 3 days or more. An inorganic adhesive composition is provided. Here, the "additional powdery oxide" refers to a powder of an oxide other than aluminum oxide. In the inorganic adhesive composition, the powdery aluminum oxide preferably contains 0.1 to 0.8% by weight of Na 2 O. In addition, the present invention has a particle size of 5 to 300 mμ.
Of the colloidal silica as a main component of 6 to 20% by weight in terms of solid content, and powdered mullite having an average particle size of 1 to 30 μ in terms of solid content of 30 to 90% by weight, and an average particle size of 1 to 30 μm. Additional powdery oxide is 0 to solid content.
70% by weight and the balance water, and after the composition is kept at 50 ° C. for 3 days or more, the concentration of water-soluble Na 2 O in the composition is 300 to 1,500 pp.
m, the concentration of water-soluble Na 2 O is 400 ppm or more when converted per mullite, and the pH of the composition is in the range of 9.5 to 11.0. I will provide a. Here, the "additional powdery oxide" refers to a powder of an oxide other than mullite.
In the inorganic adhesive composition, the binder is preferably colloidal silica to which water-soluble Na 2 O is added. The colloidal silica used in the present invention preferably has a particle size of 10 to 20 mμ, and more preferably a particle size of 15 to 20 mμ. The powdery oxide used in the present invention preferably has an average particle diameter of 1 to 10 μm.
【０００９】以下、本発明の接着剤組成物の様々な側面
をいくつかの実施の形態に基づいてさらに詳しく説明す
る。Hereinafter, various aspects of the adhesive composition of the present invention will be described in more detail based on some embodiments.
【００１０】[0010]
【発明の実施の形態】本発明の無機質接着剤組成物中、
使用できるコロイダルシリカとしては、市販のもの（粒
子径５〜３００ｍμ）でよいが、好ましくは、その粒度
を調整する必要がある。好ましい粒子径の範囲は、一般
的に１０〜２０ｍμであり、粒子径が１０ｍμ未満であ
ると、コロイダルシリカの安定性が悪く（グル化が起こ
りやすい）高濃度のものが得られにくいため、接着剤と
して使用すると接着部に亀裂が入りやすくなる。なお、
コロイダルシリカは他の珪酸塩系あるいは燐酸塩系バイ
ンダに比べ、結合力が小さいため通常の条件下できるだ
け高濃度の液、好ましくは３５〜４０重量％のものが用
いられる。一方、粒子径が２０ｍμを超えると接着強度
が小さくなるので好ましくない。特に好ましい粒子径の
範囲は、１５〜２０ｍμである。BEST MODE FOR CARRYING OUT THE INVENTION In the inorganic adhesive composition of the present invention,
The colloidal silica that can be used may be a commercially available one (particle size 5 to 300 mμ), but it is necessary to adjust the particle size thereof. The preferred particle size range is generally 10 to 20 mμ, and if the particle size is less than 10 mμ, the stability of the colloidal silica is poor (prone to gluing) and a high concentration is difficult to obtain, so adhesion When it is used as an agent, cracks easily occur in the adhesive part. In addition,
Colloidal silica has a smaller binding force than other silicate-based or phosphate-based binders, so that a liquid having a concentration as high as possible under normal conditions, preferably 35-40% by weight, is used. On the other hand, if the particle size exceeds 20 mμ, the adhesive strength becomes small, which is not preferable. A particularly preferable range of particle diameter is 15 to 20 mμ.
【００１１】組成物中のコロイダルシリカの割合は、固
形分換算で６〜２０重量％とされる。割合が６重量％未
満となると、バインダとしての作用が不十分となり機械
的強度が低下し十分な接着力が得られない。一方、２０
重量％を超すと一般に接着部の接着力は増加するが、充
填剤（フィラー）の割合が減少するため接着部に亀裂が
入りやすくなり、加えて接着部の機械的強度が小さくな
るという不都合を生じるので好ましくない。The proportion of colloidal silica in the composition is 6 to 20% by weight in terms of solid content. If the proportion is less than 6% by weight, the action as a binder becomes insufficient, the mechanical strength is lowered, and sufficient adhesive force cannot be obtained. On the other hand, 20
Generally, if the amount exceeds 50% by weight, the adhesive strength of the adhesive part increases, but since the proportion of the filler (filler) decreases, cracks tend to occur in the adhesive part, and in addition, the mechanical strength of the adhesive part decreases. It is not preferable because it occurs.
【００１２】組成物中フィラーとして添加される粉末状
酸化物としては、アルミナ、ムライト、石英、石英ガラ
ス、ジルコニア、珪酸ジルコニウム、珪砂、珪酸アルミ
ニウム、コージェライト等を挙げることができる。前記
のもののうち、アルミナおよびムライトが特に好まし
い。粉末状酸化物は単独または混合物として用いること
ができる。Examples of the powdered oxide added as a filler in the composition include alumina, mullite, quartz, quartz glass, zirconia, zirconium silicate, silica sand, aluminum silicate, cordierite and the like. Of the above, alumina and mullite are particularly preferred. The powdered oxide can be used alone or as a mixture.
【００１３】粉末状酸化物の平均粒子径は、１〜３０μ
とされる。平均粒子径が１μ未満になると乾燥時におけ
る接着剤の乾燥収縮が大きくなり接着層に亀裂を生じ、
接着強度も小さくなり、加えて接着剤の可使時間が著し
く短くなるという不都合を生じる。一方、３０μを超す
と接着強度が低下し、加えて接着剤施工の際の作業性が
低下するという不都合を生じる。また、自動充填性など
の作業性も低下する。特に好ましい平均粒子径の範囲
は、１〜１０μである。The powdery oxide has an average particle size of 1 to 30 μm.
It is said. If the average particle size is less than 1 μ, the drying shrinkage of the adhesive during drying becomes large and cracks occur in the adhesive layer,
The adhesive strength is reduced, and in addition, the pot life of the adhesive is significantly shortened. On the other hand, if it exceeds 30 μ, the adhesive strength is lowered, and in addition, the workability at the time of applying the adhesive is lowered. In addition, workability such as automatic filling is also reduced. A particularly preferable range of the average particle size is 1 to 10 μm.
【００１４】接着剤組成物中の粉末状酸化物の混合割合
は、一般的に固形分換算で３０〜９０重量％、好ましく
は５０〜９０重量％とされる。粉末状酸化物の割合が３
０重量％未満となると接着剤の強度の低下、あるいは接
着部に亀裂が入りやすくなるので好ましくなく、一方９
０重量％を超すと接着性、機械的強度が著しく低下する
ので好ましくない。The mixing ratio of the powdery oxide in the adhesive composition is generally 30 to 90% by weight, preferably 50 to 90% by weight in terms of solid content. The ratio of powdered oxide is 3
If it is less than 0% by weight, it is not preferable because the strength of the adhesive is lowered, or cracks are likely to occur in the adhesive portion.
If it exceeds 0% by weight, the adhesiveness and the mechanical strength are remarkably lowered, which is not preferable.
【００１５】前記の市販コロイダルシリカは、少量のＮ
ａ2Ｏ（通常０．３〜０．４重量％）で安定化されてい
るが、このＮａ2Ｏが粉末状酸化物と混合されると反応
しコロイダルシリカを不安定化することがある。その結
果、増粘、固化等を生じたりするが、これら増粘、固化
の程度は粉末状酸化物の種類、粒度、表面状態等に影響
を受けるので、一義的に評価することが困難である。The commercial colloidal silica described above contains a small amount of N.
It is stabilized with a 2 O (usually 0.3 to 0.4% by weight), but when this Na 2 O is mixed with the powdered oxide, it may react to destabilize the colloidal silica. As a result, thickening, solidification, etc. may occur, but the degree of thickening, solidification is affected by the type, particle size, surface state, etc. of the powdered oxide, making it difficult to uniquely evaluate. .
【００１６】本発明者らは、コロイダルシリカと粉末状
酸化物を混合し、接着剤組成物を調製した後に、５０℃
で３日以上保持した後、水抽出を行ったときの水溶性の
Ｎａ2Ｏ（Ｎａイオンを酸化物として算出）が接着剤基
準で３００〜１，５００ｐｐｍであり、かつ組成物のｐ
Ｈが９．５〜１１．０のとき組成物は長期間安定で３ケ
月以上を増結、固化を示さないことを見出した。コロイ
ダルシリカおよび粉末状酸化物から成る組成物が前記の
条件を満たさない場合、水溶性Ｎａ2Ｏまたはその前駆
体を組成物に添加し、５０℃３日以上保持後の水溶性Ｎ
ａ2Ｏ濃度および組成物のｐＨを前記の範囲に調節する
必要がある。The inventors of the present invention mixed the colloidal silica and the powdered oxide to prepare an adhesive composition, which was then heated to 50 ° C.
After being stored for 3 days or longer at room temperature, water-soluble Na 2 O (calculated as Na ion as an oxide) when extracted with water is 300 to 1,500 ppm based on the adhesive, and p of the composition is
It was found that when H was 9.5 to 11.0, the composition was stable for a long period of time, accumulated for 3 months or more, and did not show solidification. When the composition consisting of colloidal silica and powdered oxide does not satisfy the above conditions, water-soluble Na 2 O or its precursor is added to the composition, and water-soluble N 2 after holding at 50 ° C. for 3 days or more is added.
It is necessary to adjust the a 2 O concentration and the pH of the composition within the above range.
【００１７】通常、粉末状酸化物はＮａ2Ｏを表面に吸
着あるいはＮａ2Ｏと反応するため水溶性Ｎａ2Ｏおよび
ｐＨの両方とも前記の範囲に調整することには困難を伴
う。そこで本発明に従えば、ＮａＯＨ（苛性ソーダ）を
添加することにより水溶性Ｎａ2Ｏ、ｐＨを所定範囲に
なるよう調整することができる。ＮａＯＨの添加につい
ては、結果として、バインダに添加されていればよく、
バインダそのものに予め添加し、粉末状酸化物を混合す
る方法、あるいはバインダとフィラーを混合した後、接
着剤組成物を製造する段階で添加する方法などがあり、
添加方法そのものに特に限定はない。Usually, the powdery oxide adsorbs Na 2 O on the surface or reacts with Na 2 O, so that it is difficult to adjust both the water-soluble Na 2 O and the pH within the above range. Therefore, according to the present invention, by adding NaOH (caustic soda), the water-soluble Na 2 O and pH can be adjusted within a predetermined range. As for the addition of NaOH, as a result, it may be added to the binder,
There is a method of adding the powdery oxide in advance to the binder itself, a method of mixing the binder and the filler, and a method of adding the binder at the stage of producing the adhesive composition,
The addition method itself is not particularly limited.
【００１８】使用される粉末状酸化物によっては、接着
剤組成物中にＮａ2Ｏを放出するものもあり、このよう
な場合には水溶性Ｎａ2Ｏを添加する必要はない。例と
してはある種のアルミナ粉末等が挙げられる。たとえば
市販のアルミナの中には、水溶性のＮａ2Ｏをすでに含
有しているものがあり、このような製品を使用すると接
着剤組成物の水分散系においてＮａ2Ｏは徐々に水分に
溶解し、長期間に亘り水溶性のＮａ2Ｏを放出するので
結果的にはＮａ2Ｏを前記のように添加したのと同じ効
果が得られる。粉末酸化物として前記のようなアルミナ
を使用する場合、アルミナ中にＮａ2Ｏとして０．１〜
０．８重量％を含むものが好ましい。Ｎａ2Ｏの含有量
が０．１重量％未満であると水溶性Ｎａ2Ｏの放出効果
が少なく、また逆に０．８重量％を超すと水溶性Ｎａ2
Ｏの放出量が多すぎ接着剤組成物の安定化が阻害される
ことがある。このような場合、特に本発明の接着剤組成
物をガラス材料の接着に用いるとガラスに対し耐食性が
劣化することなどのために好ましくない状況になる。使
用するアルミナが低ソーダアルミナ（Ｎａ2Ｏの含有量
が低い）場合、前記のように水溶性Ｎａ2Ｏの前駆体
（たとえばＮａＯＨ）を接着剤組成物に添加して水溶性
Ｎａ2ＯおよびｐＨに関して所定の条件を満たすように
することができる。Depending on the powdered oxide used, some may release Na 2 O into the adhesive composition and in such cases it is not necessary to add water soluble Na 2 O. Examples include certain alumina powders and the like. For example, some commercially available alumina already contains water-soluble Na 2 O, and when such a product is used, Na 2 O gradually dissolves in water in the water dispersion system of the adhesive composition. However, since water-soluble Na 2 O is released over a long period of time, the same effect as adding Na 2 O as described above can be obtained as a result. When the above-mentioned alumina is used as the powdered oxide, Na 2 O in the alumina is 0.1 to 0.1%.
Those containing 0.8% by weight are preferable. Na 2 O content less release effect of the water-soluble Na 2 O is less than 0.1 wt%, also more than 0.8% by weight on the contrary aqueous Na 2
The amount of released O is too large, which may hinder the stabilization of the adhesive composition. In such a case, particularly when the adhesive composition of the present invention is used for adhering a glass material, it is not preferable because the corrosion resistance of the glass is deteriorated. If the alumina used is low soda alumina (low Na 2 O content), a water soluble Na 2 O precursor (eg, NaOH) is added to the adhesive composition as described above to remove water soluble Na 2 O and It is possible to satisfy a predetermined condition regarding pH.
【００１９】本発明の別の実施の形態として、粉末状酸
化物にムライトを使用できる。ムライトは、熱膨張係数
がランプ用のガラスに近く、またコロイダルシリカとの
適合性が良く、接着強度が強いため、ランプの口金用の
接着剤のフィラーとして使用されてきた。市販のムライ
ト粉末は、前記のソーダアルミナと同程度のＮａ2Ｏを
含有している。しかしながら、ムライトの場合水溶性Ｎ
ａ2Ｏを放出することなく、むしろ組成物中でＮａ2Ｏを
取込むことが見出された。このような取込み効果を補償
するために、水溶性Ｎａ2ＯおよびｐＨに関して前記の
所定範囲にある接着剤組成物を調製するためには、Ｎａ
ＯＨをフィラーであるムライト粉末に添加する必要があ
る。この場合、５０℃、３日間組成物を保持した後、水
溶性Ｎａ2Ｏが組成物中で濃度３００〜１，５００ｐｐ
ｍであり、かつムライト当たりに換算すると４００ｐｐ
ｍ以上になるように水溶性Ｎａ2Ｏの前駆体（たとえ
ば、ＮａＯＨ）を添加すればよい。添加量がこのような
範囲を超える量で使用すると、前記と同様ガラスに対し
て耐食性が劣化するなどの悪影響がある。As another embodiment of the present invention, mullite can be used for the powdered oxide. Mullite has been used as a filler for adhesives for lamp bases because it has a thermal expansion coefficient close to that of glass for lamps, good compatibility with colloidal silica, and strong adhesive strength. The commercially available mullite powder contains Na 2 O at the same level as the soda alumina. However, in the case of mullite, water-soluble N
It has been found to incorporate Na 2 O in the composition without releasing a 2 O. In order to compensate for such incorporation effects, Na in order to prepare an adhesive composition in the above-mentioned predetermined range with respect to water-soluble Na 2 O and pH, Na
It is necessary to add OH to the mullite powder that is a filler. In this case, after the composition was held at 50 ° C. for 3 days, water-soluble Na 2 O had a concentration of 300 to 1,500 pp in the composition.
m and 400pp when converted per mullite
A water-soluble Na 2 O precursor (for example, NaOH) may be added so that the amount becomes m or more. If it is used in an amount exceeding the above range, there is an adverse effect such as deterioration in corrosion resistance of the glass as described above.
【００２０】本発明において、水溶性Ｎａ2Ｏの濃度を
接着剤組成物が５０℃で３日間保持された後、評価した
理由は、保持時間が少なくとも３日間であれば評価が可
能であるからである。すなわち、通常、接着剤組成物中
で水溶性Ｎａ2Ｏの溶出、吸収は（粉末状酸化物に対す
る吸収）約３日間で平衡状態に近くなり、それ以後の溶
出、吸収は緩慢となる。もちろん、３日以上の期間、接
着剤組成物を前記条件で保持することも可能であるが、
実用上は接着剤組成物を調製後、寝かせる期間が短いほ
ど好ましいのでそれ以上長期に亘って保持する利点は少
ない。水溶性Ｎａ2ＯおよびｐＨの評価方法について
は、以下の実施例中に詳しく述べる。In the present invention, the reason why the concentration of water-soluble Na 2 O was evaluated after the adhesive composition was held at 50 ° C. for 3 days was that the holding time was at least 3 days. Is. That is, usually, the elution and absorption of water-soluble Na 2 O in the adhesive composition is close to the equilibrium state (absorption to the powdery oxide) in about 3 days, and the elution and absorption thereafter are slow. Of course, it is possible to hold the adhesive composition under the above conditions for a period of 3 days or more,
Practically, it is preferable that the adhesive composition is prepared and laid down for a shorter period of time, so that there is little advantage of holding it for a longer period. The method for evaluating water-soluble Na 2 O and pH will be described in detail in the examples below.
【００２１】本発明の接着剤組成物には、必要に応じ他
の補助剤を添加することができる。このような添加可能
な補助剤としては、増粘剤、沈降防止剤としてベントナ
イト等の粘土類、亀裂防止剤として、無機質繊維、また
は熱膨張係数調整剤としてペタライト、スポテュメン等
の低熱膨張係数を有する充填剤等を用いることができ
る。さらに、本発明の接着剤組成物は水の添加により任
意の粘度とすることができる。組成物の粘度は用途に応
じて調整するが、通常はＢ型粘度計で５，０００〜２０
０，０００ｃｐｓの範囲が好ましい。If necessary, other auxiliary agents can be added to the adhesive composition of the present invention. Such auxiliary agents that can be added include thickeners, clays such as bentonite as an anti-settling agent, inorganic fibers as an anti-cracking agent, or low thermal expansion coefficients such as petalite and spoteumen as a thermal expansion coefficient adjusting agent. A filler or the like can be used. Further, the adhesive composition of the present invention can be made to have an arbitrary viscosity by adding water. Although the viscosity of the composition is adjusted depending on the use, it is usually 5,000 to 20 with a B type viscometer.
A range of 10,000 cps is preferred.
【００２２】本発明の接着剤組成物を製造するに際し
て、バインダとフィラーおよびその他の補助剤の混合方
法としては公知の方法を用いることができ、通常の羽根
撹拌、ライカイ器などによる混合、ボールミルなどによ
る混合等が使用できる。In the production of the adhesive composition of the present invention, a known method can be used as a method for mixing the binder, the filler and the other auxiliary agent, such as ordinary blade stirring, mixing with a reiki machine, ball mill, etc. Can be used.
【００２３】本発明の接着剤組成物により接着された接
着部は、常温で乾燥することにより充分な硬化を起こす
が、硬化時間を短縮するのが望まれる場合には、加熱硬
化を行ってもよく、そのような加熱温度は任意に設定す
ることができる。本発明の接着剤組成物は、特にランプ
を構成するガラス材料と口金金属部の接着に利用する
と、接着強度の優れたランプを得ることができる。この
場合、従来の有機質バインダを含む接着剤、シリコン樹
脂、セメントまたは低融点ガラスを使用した従来のラン
プ接着部に比較して、本発明を利用すると、耐熱性、耐
熱衝撃性についても顕著に優れた接着部を形成すること
ができる。The adhesive portion adhered by the adhesive composition of the present invention is sufficiently cured by drying at room temperature, but if it is desired to shorten the curing time, it may be cured by heating. Well, such heating temperature can be set arbitrarily. When the adhesive composition of the present invention is used for adhering the glass material forming the lamp and the metal part of the base, a lamp having excellent adhesive strength can be obtained. In this case, compared with the conventional adhesive agent containing an organic binder, silicon resin, cement or a conventional lamp adhesive section using low melting point glass, the present invention is used, the heat resistance and thermal shock resistance are remarkably excellent. Bonded portions can be formed.
【００２４】以下に実施例により本発明をさらに詳細に
説明するが本発明はこれらによって制限されるものでは
ない。なお、実施例中の部および％は全て重量基準を示
す。The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. All parts and% in the examples are based on weight.
【００２５】実施例１ 平均粒子径１７．５ｍμで、固形分濃度４０％のコロイ
ダルシリカを２３．３部と、５％のＮａＯＨ水溶液の１
部とを混合した。この混合液を平均粒子径６．２μのム
ライト粉末７５．７部に加え混合し、本発明の無機質接
着剤組成物を製造した。得られた組成物の粘度は、約３
０，０００ｃｐｓ、ｐＨは１０．５であった。製造直後
の組成物をガラス容器に入れ、５０℃で３日間保持し
た。保持後の粘度は２９，０００ｃｐｓでｐＨは９．８
であった。さらに、組成物１部に対し、水を９部加え、
充分に混合した後、遠心沈降分離し、上澄み液を濾過
し、Ｎａ2Ｏを分析した（分析方法については後述）。
Ｎａ2Ｏは組成物全体を基準にして５２０ｐｐｍ、使用
したムライト粉末を基準にして６９０ｐｐｍであった。
本例の組成物は、室温で４ケ月放置したところ、粘度は
３２，０００ｃｐｓと安定で、特に使用に際しての問題
はなかった。Example 1 23.3 parts of colloidal silica having an average particle size of 17.5 mμ and a solid content of 40% and 1% of a 5% NaOH aqueous solution.
Parts were mixed. This mixed solution was added to and mixed with 75.7 parts of mullite powder having an average particle size of 6.2 μ to produce the inorganic adhesive composition of the present invention. The viscosity of the resulting composition is about 3
The pH was 10,000 cps and 10.5. The composition immediately after production was put in a glass container and kept at 50 ° C. for 3 days. Viscosity after holding is 29,000 cps and pH is 9.8.
Met. Furthermore, 9 parts of water was added to 1 part of the composition,
After thoroughly mixing, the mixture was centrifuged and separated, and the supernatant was filtered and analyzed for Na 2 O (the analysis method will be described later).
Na 2 O was 520 ppm based on the total composition and 690 ppm based on the mullite powder used.
When the composition of this example was allowed to stand at room temperature for 4 months, the viscosity was stable at 32,000 cps, and there was no problem in use.
【００２６】実施例２、３ コロイダルシリカ、ムライトの使用量を表１に示す量と
した以外、実施例１と同様にして本発明の無機質接着剤
組成物を製造した。組成物中の水溶性Ｎａ2Ｏの濃度、
組成物の粘度およびｐＨを測定した。それらの結果を表
１に併記する。Examples 2 and 3 An inorganic adhesive composition of the present invention was produced in the same manner as in Example 1 except that the amounts of colloidal silica and mullite used were those shown in Table 1. The concentration of water-soluble Na 2 O in the composition,
The viscosity and pH of the composition were measured. The results are shown in Table 1.
【００２７】実施例４ 平均粒子径１７．５ｍμで、固形分濃度４０％のコロイ
ダルシリカを２３．５部と、５％のＮａＯＨ水溶液の１
部とを混合した。この混合液を平均粒子径６．５μのア
ルミナ粉末７５．５部に加え混合し、本発明の無機質接
着剤組成物を製造した。なお、使用したアルミナ粉末中
のＮａ2Ｏ含有量は０．２５％であった。得られた組成
物の粘度は、約２７，０００ｃｐｓ、ｐＨは１０．３で
あった。製造直後の組成物をガラス容器に入れ、５０℃
で３日間保持した。保持後の粘度は２８，０００ｃｐｓ
でｐＨは１０．１であった。さらに、組成物１部に対
し、水を９部加え、充分に混合した後、遠心沈降分離
し、上澄み液を濾過し、Ｎａ2Ｏを分析した。Ｎａ2Ｏは
組成物を基準にして８５０ｐｐｍであった。本例の組成
物は、室温で４ケ月放置したところ、粘度は２９，００
０ｃｐｓと安定で、特に使用に際しての問題はなかっ
た。Example 4 23.5 parts of colloidal silica having an average particle size of 17.5 mμ and a solid content concentration of 40% and 1% of a 5% NaOH aqueous solution.
Parts were mixed. This mixed solution was added to and mixed with 75.5 parts of alumina powder having an average particle diameter of 6.5μ to produce the inorganic adhesive composition of the present invention. The content of Na 2 O in the used alumina powder was 0.25%. The obtained composition had a viscosity of about 27,000 cps and a pH of 10.3. Put the composition immediately after manufacturing in a glass container and
Held for 3 days. Viscosity after holding is 28,000 cps
The pH was 10.1. Further, 9 parts of water was added to 1 part of the composition, and after sufficiently mixing, centrifugal separation was carried out, the supernatant was filtered, and Na 2 O was analyzed. Na 2 O was 850 ppm based on the composition. The composition of this example had a viscosity of 29.00 when left at room temperature for 4 months.
It was stable at 0 cps, and there was no problem in use.
【００２８】実施例５ 平均粒子径１７．５ｍμで、固形分濃度４０％のコロイ
ダルシリカを２４．６部、平均粒子径５．９μのアルミ
ナ粉末７５．４部に加え混合し、本発明の無機質接着剤
組成物を製造した。なお、使用したアルミナ粉末中のＮ
ａ2Ｏ含有量は０．２５％であった。得られた組成物の
粘度は約２９，０００ｃｐｓ、ｐＨは１０．２であっ
た。製造直後の組成物をガラス容器に入れ、５０℃で３
日間保持した。保持後の粘度は３１，０００ｃｐｓでｐ
Ｈは９．８であった。さらに、組成物１部に対し、水を
９部加え、充分に混合した後、遠心沈降分離し、上澄み
液を濾過し、Ｎａ2Ｏを分析した。Ｎａ2Ｏは組成物を基
準にして６５０ｐｐｍであった。本例の組成物は、室温
で４ケ月放置したところ、粘度は３０，０００ｃｐｓと
安定で、特に使用に際しての問題はなかった。Example 5 24.6 parts of colloidal silica having an average particle size of 17.5 mμ and a solid content of 40% was added to 75.4 parts of alumina powder having an average particle size of 5.9 μ and mixed to obtain the inorganic material of the present invention. An adhesive composition was produced. In addition, N in the used alumina powder
The a 2 O content was 0.25%. The resulting composition had a viscosity of about 29,000 cps and a pH of 10.2. The composition immediately after production was put in a glass container and kept at 50 ° C. for 3 days.
Held for days. Viscosity after holding is 31,000 cps and p
H was 9.8. Further, 9 parts of water was added to 1 part of the composition, and after sufficiently mixing, centrifugal separation was carried out, the supernatant was filtered, and Na 2 O was analyzed. Na 2 O was 650 ppm based on the composition. The composition of this example had a stable viscosity of 30,000 cps when left at room temperature for 4 months, and there was no problem in use.
【００２９】実施例６ 平均粒子径１１．５ｍμで、固形分濃度４０％のコロイ
ダルシリカを２４．１部、平均粒子径５．９μのアルミ
ナ粉末７５．９部に加え混合し、本発明の無機質接着剤
組成物を製造した。なお、使用したアルミナ粉末中のＮ
ａ2Ｏ含有量は０．２５％であった。得られた組成物の
粘度は、約２９，０００ｃｐｓ、ｐＨは１０．２であっ
た。製造直後の組成物をガラス容器に入れ、５０℃で３
日間保持した。保持後の粘度は３１，０００ｃｐｓでｐ
Ｈは９．８であった。さらに、組成物１部に対し、水を
９部加え、充分に混合した後、遠心沈降分離し、上澄み
液を濾過し、Ｎａ2Ｏを分析した。Ｎａ2Ｏは組成物を基
準にして６５０ｐｐｍであった。本例の組成物は、室温
で２ケ月放置したところ、粘度は３０，０００ｃｐｓと
安定で、特に使用に際しての問題はなかった。しかし、
４ケ月を経過すると粘度は６５，０００ｃｐｓと増粘傾
向を示した。Example 6 24.1 parts of colloidal silica having an average particle diameter of 11.5 mμ and a solid content of 40% and 75.9 parts of alumina powder having an average particle diameter of 5.9 μ were added to and mixed with the inorganic material of the present invention. An adhesive composition was produced. In addition, N in the used alumina powder
The a 2 O content was 0.25%. The composition obtained had a viscosity of about 29,000 cps and a pH of 10.2. The composition immediately after production was put in a glass container and kept at 50 ° C. for 3 days.
Held for days. Viscosity after holding is 31,000 cps and p
H was 9.8. Further, 9 parts of water was added to 1 part of the composition, and after sufficiently mixing, centrifugal separation was carried out, the supernatant was filtered, and Na 2 O was analyzed. Na 2 O was 650 ppm based on the composition. When the composition of this example was left at room temperature for 2 months, the viscosity was stable at 30,000 cps, and there was no problem in use. But,
After 4 months, the viscosity showed a tendency to increase to 65,000 cps.
【００３０】比較例１ 平均粒子径１７．５ｍμで、固形分濃度４０％のコロイ
ダルシリカを２３．１部と、平均粒子径６．２μのムラ
イト粉末７５．９部とを混合し、無機質接着剤組成物を
製造した。得られた本例の組成物の粘度は、約２８，０
００ｃｐｓ、ｐＨは９．８であった。製造直後の組成物
をガラス容器に入れ、５０℃で３日間保持した。保持後
の粘度は９０，０００ｃｐｓでｐＨは８．２であった。
さらに、組成物１部に対し、水を９部加え、充分に混合
した後、遠心沈降分離し、上澄み液を濾過し、Ｎａ2Ｏ
を分析した。Ｎａ2Ｏは組成物を基準にして１７０ｐｐ
ｍ、ムライト粉末を基準にして２２０ｐｐｍであった。
本例の組成物は、室温で２週間放置したところ、粘度は
１００，０００ｃｐｓ以上であり固結寸前で、使用でき
なかった。Comparative Example 1 23.1 parts of colloidal silica having an average particle size of 17.5 mμ and a solid content of 40% and 75.9 parts of mullite powder having an average particle size of 6.2 μ were mixed to form an inorganic adhesive. A composition was produced. The viscosity of the obtained composition of this example is about 28,0.
It was 00 cps and pH was 9.8. The composition immediately after production was put in a glass container and kept at 50 ° C. for 3 days. After holding, the viscosity was 90,000 cps and the pH was 8.2.
Further, 9 parts of water was added to 1 part of the composition, mixed sufficiently, centrifuged and separated, and the supernatant was filtered, and Na 2 O was added.
Was analyzed. Na 2 O is 170 pp based on the composition
It was 220 ppm based on m and mullite powder.
When the composition of this example was allowed to stand at room temperature for 2 weeks, its viscosity was 100,000 cps or more, and it was just before consolidation, and could not be used.
【００３１】比較例２ コロイダルシリカ、ムライトの使用量を表１に示す量と
した以外、比較例１と同様にして無機質接着剤組成物を
製造した。組成物中の水溶性Ｎａ2Ｏの濃度、組成物の
粘度およびｐＨを測定した。それらの結果を表１に併記
する。Comparative Example 2 An inorganic adhesive composition was produced in the same manner as in Comparative Example 1 except that the amounts of colloidal silica and mullite used were those shown in Table 1. The concentration of water-soluble Na 2 O in the composition, the viscosity of the composition and the pH were measured. The results are shown in Table 1.
【００３２】[0032]
【表１】 [Table 1]
【００３３】物性試験 実施例、比較例、表１に示す接着剤組成物の各物性につ
いては、以下の要領で測定した。 ａ）粘度 Ｂ型粘度計を使用して測定した。 ｂ）粉末状酸化物の粒子径 レーザ回折型粘度計（島津製作所製）を使用して測定し
た。 ｃ）コロイダルシリカの粒子径 コロイダルシリカを酸でｐＨ２〜３に下げ、蒸発乾固
（１１０〜１３０℃）後、洗浄、乾燥したものの比表面
積を測定し、その値より粒子径を逆算した。 ｄ）５０℃保持後の水溶性Ｎａ2Ｏ 組成物試料をポリ容器に入れ、密封した上で５０℃で３
日間保持した。保持後、一定量試料をサンプリングし、
１０倍量の水で希釈し、充分に撹拌した後、遠心沈降分
離にかけ、固液を分離し、上澄み液を採取した。上澄み
液中のＮａ2Ｏ量を原子吸光法により測定した。 ｅ）５０℃保持後のｐＨ ｄ）に記載のようにして５０℃で３日間保持した試料を
室温まで冷却し、ｐＨメータで測定した。 Physical Properties Test The physical properties of the adhesive compositions shown in Examples and Comparative Examples and Table 1 were measured in the following manner. a) Viscosity It was measured using a B-type viscometer. b) Particle diameter of powdered oxide It was measured using a laser diffraction type viscometer (manufactured by Shimadzu Corporation). c) Particle diameter of colloidal silica The pH of colloidal silica was lowered to pH 2 to 3 with an acid, and after evaporating to dryness (110 to 130 ° C), washing and drying, the specific surface area was measured, and the particle diameter was calculated back from the value. d) A water-soluble Na 2 O composition sample after holding at 50 ° C was placed in a plastic container, sealed, and then kept at 50 ° C for 3 hours.
Held for days. After holding, sample a fixed amount of sample,
After diluting with 10 times the amount of water and stirring sufficiently, it was subjected to centrifugal sedimentation to separate the solid and liquid, and the supernatant was collected. The amount of Na 2 O in the supernatant was measured by the atomic absorption method. e) pH after holding at 50 ° C. The sample held at 50 ° C. for 3 days as described in d) was cooled to room temperature and measured with a pH meter.
【００３４】[0034]
【発明の効果】以上のように本発明によれば、無機質接
着剤組成物中のバインダであるコロイダルシリカが安定
化され、ゲル化（増粘、固化等）が起こらないため、組
成物が長期間にわたり、保存、かつ使用可能である。As described above, according to the present invention, colloidal silica, which is a binder in the inorganic adhesive composition, is stabilized and gelation (thickening, solidification, etc.) does not occur, so that the composition is long-lived. It can be stored and used for a period of time.
【００３５】さらに本発明によれば、無機質接着剤組成
物を冷却保存する必要がなく、保管コスト、輸送コスト
を従来技術の接着剤組成物より大幅に下げることができ
る。Further, according to the present invention, it is not necessary to cool and store the inorganic adhesive composition, and the storage cost and the transportation cost can be significantly reduced as compared with the adhesive compositions of the prior art.
Claims (8)
カを主成分とするバインダを固形分換算で６〜２０重量
％と、平均粒子径１〜３０μの粉末状酸化物を固形分換
算で５０〜９０重量％と、残部として水とを含んで成る
組成物であり、かつ該組成物を５０℃で３日以上保持し
た後、組成物中の水溶性Ｎａ2Ｏの濃度が３００〜１，
５００ｐｐｍであり、そして組成物のｐＨが９．５〜１
１．０の範囲にあることを特徴とする無機質接着剤組成
物。1. A binder containing colloidal silica as a main component having a particle size of 5 to 300 μm in an amount of 6 to 20% by weight in terms of solid content, and a powdery oxide having an average particle size of 1 to 30 μ in an amount of 50 to 90 in terms of solid content. The composition comprises, by weight, and water as the balance, and after the composition is kept at 50 ° C. for 3 days or more, the concentration of water-soluble Na 2 O in the composition is 300 to 1,
500 ppm and the pH of the composition is 9.5 to 1
An inorganic adhesive composition characterized by being in the range of 1.0.
カを主成分とするバインダを固形分換算で６〜２０重量
％と、平均粒子径１〜３０μの粉末状酸化アルミニウム
を固形分換算で３０〜９０重量％と、平均粒子径１〜３
０μの付加的粉末状酸化物を固形分換算で０〜７０重量
％と、残部として水とを含んで成る組成物であり、かつ
該組成物を５０℃で３日以上保持した後、組成物中の水
溶性Ｎａ2Ｏの濃度が３００〜１，５００ｐｐｍであ
り、そして組成物のｐＨが９．５〜１１．０の範囲にあ
ることを特徴とする無機質接着剤組成物。2. A binder having a particle diameter of 5 to 300 μm and containing colloidal silica as a main component in a solid content of 6 to 20% by weight, and an aluminum oxide powder having an average particle diameter of 1 to 30 μ in a solid content of 30 to 90. % By weight, average particle size 1-3
A composition comprising 0 to 70% by weight of a solid oxide of an additional powdery oxide, and water as the balance, and the composition after being kept at 50 ° C. for 3 days or more. An inorganic adhesive composition, wherein the concentration of water-soluble Na 2 O in the composition is 300 to 1,500 ppm, and the pH of the composition is in the range of 9.5 to 11.0.
０．１〜０．８重量％含有する請求項２記載の無機質接
着剤組成物。3. The inorganic adhesive composition according to claim 2 , wherein the powdery aluminum oxide contains 0.1 to 0.8% by weight of Na 2 O.
カを主成分とするバインダを固形分換算で６〜２０重量
％と、平均粒子径１〜３０μの粉末状ムライトを固形分
換算で３０〜９０重量％と、平均粒子径１〜３０μの付
加的粉末状酸化物を固形分換算で０〜７０重量％と、残
部として水とを含んで成る組成物であり、かつ該組成物
を５０℃で３日以上保持した後、組成物中の水溶性Ｎａ
2Ｏの濃度が３００〜１，５００ｐｐｍであり、さらに
水溶性Ｎａ2Ｏの濃度がムライト当たりに換算すると４
００ｐｐｍ以上であり、そして組成物のｐＨが９．５〜
１１．０の範囲にあることを特徴とする無機質接着剤組
成物。4. A binder containing colloidal silica having a particle diameter of 5 to 300 μm as a main component in a solid content of 6 to 20% by weight, and a powdered mullite having an average particle diameter of 1 to 30 μ in a solid content of 30 to 90% by weight. %, An additional powdery oxide having an average particle size of 1 to 30 μ, in terms of solid content of 0 to 70% by weight, and the balance of water, and the composition at 3 ° C. at 3 ° C. After holding for more than a day, water-soluble Na in the composition
The concentration of 2 O is 300 to 1,500 ppm, and the concentration of water-soluble Na 2 O is 4 when converted per mullite.
Greater than or equal to 00 ppm, and the pH of the composition is between 9.5 and
An inorganic adhesive composition characterized by being in the range of 11.0.
Ｎａ2Ｏを添加したものである請求項１または４記載の
無機質接着剤組成物。5. The inorganic adhesive composition according to claim 1, wherein the binder is colloidal silica to which water-soluble Na 2 O is added.
ｍμである請求項１〜５いずれかに記載の無機質接着剤
組成物。6. The colloidal silica has a particle size of 10 to 20.
It is m (micro | micron | mu), The inorganic adhesive composition in any one of Claims 1-5.
ｍμである請求項１〜５いずれかに記載の無機質接着剤
組成物。7. The colloidal silica has a particle size of 15 to 20.
It is m (micro | micron | mu), The inorganic adhesive composition in any one of Claims 1-5.
μである請求項１〜７いずれかに記載の無機質接着剤組
成物。8. The average particle size of the powdery oxide is 1 to 10.
The inorganic adhesive composition according to any one of claims 1 to 7, which is µ.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07439296A JP3764202B2 (en) | 1996-03-28 | 1996-03-28 | Inorganic adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07439296A JP3764202B2 (en) | 1996-03-28 | 1996-03-28 | Inorganic adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09263732A true JPH09263732A (en) | 1997-10-07 |
| JP3764202B2 JP3764202B2 (en) | 2006-04-05 |
Family
ID=13545874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07439296A Expired - Lifetime JP3764202B2 (en) | 1996-03-28 | 1996-03-28 | Inorganic adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3764202B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001329230A (en) * | 2000-05-22 | 2001-11-27 | Asahi Kagaku Kogyo Co Ltd | Inorganic adhesive composition, its manufacturing method and bonding method |
| JP2001329231A (en) * | 2000-05-22 | 2001-11-27 | Asahi Kagaku Kogyo Co Ltd | Inorganic adhesive composition, its manufacturing method and bonding method |
| JP2007063305A (en) * | 2005-08-29 | 2007-03-15 | Asahi Kagaku Kogyo Co Ltd | Adhesive composition |
-
1996
- 1996-03-28 JP JP07439296A patent/JP3764202B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001329230A (en) * | 2000-05-22 | 2001-11-27 | Asahi Kagaku Kogyo Co Ltd | Inorganic adhesive composition, its manufacturing method and bonding method |
| JP2001329231A (en) * | 2000-05-22 | 2001-11-27 | Asahi Kagaku Kogyo Co Ltd | Inorganic adhesive composition, its manufacturing method and bonding method |
| JP2007063305A (en) * | 2005-08-29 | 2007-03-15 | Asahi Kagaku Kogyo Co Ltd | Adhesive composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3764202B2 (en) | 2006-04-05 |
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