JPH0587445B2 - - Google Patents
Info
- Publication number
- JPH0587445B2 JPH0587445B2 JP61075283A JP7528386A JPH0587445B2 JP H0587445 B2 JPH0587445 B2 JP H0587445B2 JP 61075283 A JP61075283 A JP 61075283A JP 7528386 A JP7528386 A JP 7528386A JP H0587445 B2 JPH0587445 B2 JP H0587445B2
- Authority
- JP
- Japan
- Prior art keywords
- sol
- tin oxide
- conductive tin
- particles
- dispersed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002245 particle Substances 0.000 claims description 60
- 239000000843 powder Substances 0.000 claims description 54
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 39
- 229910001887 tin oxide Inorganic materials 0.000 claims description 39
- 239000007864 aqueous solution Substances 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims description 6
- 239000002612 dispersion medium Substances 0.000 claims description 4
- 239000011260 aqueous acid Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- 239000003973 paint Substances 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 11
- 239000004033 plastic Substances 0.000 description 10
- 229920003023 plastic Polymers 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 229910052787 antimony Inorganic materials 0.000 description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 etc. Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 229940087646 methanolamine Drugs 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は異種元素をドープした導電性酸化錫が
コロイド粒子として水又は親水性有機溶媒に分散
したゾルと、そのゾルの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a sol in which conductive tin oxide doped with a different element is dispersed as colloidal particles in water or a hydrophilic organic solvent, and a method for producing the sol.
［従来の技術］
無機酸化物のゾルとしては、シリカゾル、アル
ミナゾルなどが知られており、その製造法も公知
である。例えば、シリカゾルは水ガラスなどの珪
酸アルカリ塩水溶液を脱アルカリする方法によつ
て製造することができ、その他の無機酸化物ゾル
も適当な硝酸塩、塩化物或いは金属アルコキシド
を、加水分解することによつて製造することがで
きる。[Prior Art] As inorganic oxide sols, silica sol, alumina sol, etc. are known, and their production methods are also known. For example, silica sol can be produced by dealkalizing an aqueous solution of an alkali silicate salt such as water glass, and other inorganic oxide sols can also be produced by hydrolyzing appropriate nitrates, chlorides, or metal alkoxides. It can be manufactured by
しかしながら、異種元素をドープした導電性酸
化錫が、コロイド粒子として水又は有機溶媒に分
散したゾルは、従来知られておらず、従つて、そ
の製造方法も知られていない。 However, a sol in which conductive tin oxide doped with a different element is dispersed as colloidal particles in water or an organic solvent has not been known, and therefore, a method for producing the same has not been known.
［発明が解決しようとする問題点］
アンチモン、フツ素、リン、テルル、ビスマ
ス、カドミウムなどの異種元素を少量ドープさせ
た酸化錫の粉末は、導電性を有している。従つ
て、この粉末をプラスチツクや塗料に配合すれ
ば、導電性を有するプラスチツクや塗膜を得るこ
とができるが、その場合の粉末は微細であること
が好ましい。粉末が微細であれば、プラスチツク
や塗料にこれを均一に分散させることができるば
かりでなく、プラスチツクや塗料が透明な場合に
は、その透明性を損なうことがないからである。[Problems to be Solved by the Invention] Tin oxide powder doped with a small amount of different elements such as antimony, fluorine, phosphorus, tellurium, bismuth, and cadmium has electrical conductivity. Therefore, if this powder is blended into plastics or paints, conductive plastics or paint films can be obtained, but the powder in this case is preferably fine. This is because if the powder is fine, it can not only be uniformly dispersed in plastics or paints, but also, if the plastics or paints are transparent, the transparency will not be impaired.
しかしながら、異種元素をドープさせた導電性
酸化錫（以下これを単に「導電性酸化錫」と言
う。）の粉末は、一般にその粒径が数μ〜数拾μ
の範囲であるため、プラスチツクや塗料に対する
分散性は必ずしも良好ではない。従つて、導電性
酸化錫の粉末をプラスチツクや塗料に配合するに
当つては、均一混合を目的として攪拌等の機械的
操作を施すのが通例である。この機械的操作によ
つて導電性酸化錫の粉末は或る程度粉砕されるも
のの、到底コロイド次元まで細かくすることはで
きない。 However, conductive tin oxide powder doped with a different element (hereinafter simply referred to as "conductive tin oxide") generally has a particle size of several micrometers to several tens of micrometers.
Because of this, the dispersibility in plastics and paints is not necessarily good. Therefore, when blending conductive tin oxide powder into plastics or paints, it is customary to perform mechanical operations such as stirring for the purpose of uniform mixing. Although the conductive tin oxide powder is pulverized to some extent by this mechanical operation, it cannot be pulverized to the level of a colloid.
導電性酸化錫の粉末をコロイド次元まで細かく
することは、プラスチツクや塗料に対する分散性
を向上させてプラスチツクや塗膜にむらのない均
質な導電性を付与する上でも、またプラスチツク
や塗膜の透明性を維持する上でも、極めて望まし
い。しかしながら、通常のルートで入手できる導
電性酸化錫の粉末は、既述した通り、一般にその
粒径が数μ〜数拾μの範囲にあり、しかも当該粉
末は焼成と言う熱処理を受け、多少とも焼結して
いる関係で、物理的な粉砕手段ではコロイド次元
まで微細にすることが事実上不可能である。 Refinement of conductive tin oxide powder to the colloidal level improves its dispersibility in plastics and paints, giving uniform conductivity to plastics and paint films, and also improves the transparency of plastics and paint films. It is also extremely desirable for maintaining sex. However, as mentioned above, the conductive tin oxide powder that can be obtained through normal routes generally has a particle size in the range of several micrometers to several tens of micrometers, and moreover, the powder is subjected to heat treatment called calcination, so that it is more or less Because it is sintered, it is virtually impossible to make it as fine as a colloid using physical crushing means.
而して、本発明の目的の一つは、導電性酸化錫
の粉末がコロイド次元に微細化され、これがコロ
イド粒子として分散するゾル、すなわち焼成され
た、異種元素ドープした導電性酸化錫粉末を酸水
溶液又はアルカリ水溶液中で粉砕処理して得られ
た粒子がコロイド粒子として水又は親水性有機溶
媒に分散したゾルを提供することにあり、他の一
つはそうしたゾルの製造方法を提供することにあ
る。 One of the objects of the present invention is to create a sol in which conductive tin oxide powder is finely divided into colloidal dimensions and dispersed as colloidal particles, that is, a fired conductive tin oxide powder doped with a different element. Another object of the present invention is to provide a sol in which particles obtained by pulverization in an acid aqueous solution or an alkaline aqueous solution are dispersed in water or a hydrophilic organic solvent as colloidal particles, and another object is to provide a method for producing such a sol. It is in.
［問題点を解決するための手段］
本発明に係る導電性酸化錫の水性ゾルは、焼成
された導電性酸化錫の粉末を酸水溶液又はアルカ
リ水溶液中で粉砕処理することで製造することが
できる。[Means for Solving the Problems] The aqueous conductive tin oxide sol according to the present invention can be produced by pulverizing fired conductive tin oxide powder in an acid aqueous solution or an alkaline aqueous solution. .
ここで導電性酸化錫の粉末とは、アンチモン、
フツ素、リン、テルル、ビスマス、カドミウムな
どの元素の一種又は二種以上を少量ドープさせた
酸化錫の粉末を意味するが、こうした粉末の製造
方法は公知であつて、例えば塩化錫と塩化アンチ
モンを溶解させたアルコール溶液、塩酸水溶液も
しくはアセトン溶液を、加熱水中に加えて加水分
解し、生成した沈澱を乾燥、焼成することによ
り、アンチモンがドープされた導電性酸化錫粉末
を製造することができる（特開昭56−156606号公
報参照）。また錫化合物およびアンチモン化合物
の水溶液をpH8〜12の条件下に徐々に加水分解し
てアンチモン含有錫化合物がコロイド粒子として
含有するゾルを生成させ、次いでこのゾルを乾
燥、焼成することにより、導電性酸化錫の粉末を
製造することができる。 Here, conductive tin oxide powder refers to antimony,
It refers to tin oxide powder doped with a small amount of one or more of the elements such as fluorine, phosphorus, tellurium, bismuth, and cadmium. The manufacturing method of such powder is known, for example, tin chloride and antimony chloride. Conductive tin oxide powder doped with antimony can be produced by adding an alcohol solution, an aqueous hydrochloric acid solution, or an acetone solution dissolved in antimony to heated water for hydrolysis, and drying and calcining the resulting precipitate. (Refer to Japanese Patent Application Laid-open No. 156606/1983). In addition, by gradually hydrolyzing an aqueous solution of a tin compound and an antimony compound under conditions of pH 8 to 12 to generate a sol containing antimony-containing tin compounds as colloidal particles, and then drying and baking this sol, conductive properties can be obtained. Tin oxide powder can be produced.
本発明に、ここに例示したものも含めて公知の
方法で製造された導電性酸化錫の粉末がいずれも
使用可能であるが、これらの粉末には導電性を付
与する目的で焼成処理が施されている関係で、導
電性酸化錫の一次粒子は焼結した状態にあり、こ
のため導電性酸化錫の粉末は、その粒径が数μ〜
数拾μの範囲にある。導電性を付与するための焼
成処理としては、通常の焼成処理条件が採用可能
で、例えば300℃以上好ましくは400〜800℃の温
度で0.5〜５時間処理される。本発明によれば、
こうした焼成された導電性酸化錫の粉末が酸水溶
液又はアルカリ水溶液中で粉砕処理される。酸水
溶液又はアルカリ水溶液に対する粉末の添加量
は、水溶液60重量部当り40重量部以下とすること
が好ましい。余り多量の粉末を添加すると、個々
の粉末に対して酸又はアルカリを平均に作用させ
ることが困難であるためゾルが難しく、ゾル化が
可能でもその状態を安定に保持できないからであ
る。 In the present invention, any conductive tin oxide powder produced by a known method, including those exemplified here, can be used, but these powders may be subjected to a firing treatment for the purpose of imparting conductivity. Because of this, the primary particles of conductive tin oxide are in a sintered state, and therefore conductive tin oxide powder has a particle size of several microns to
It is in the range of several tens of microns. As the firing treatment for imparting conductivity, usual firing treatment conditions can be employed, for example, treatment is performed at a temperature of 300°C or higher, preferably 400 to 800°C, for 0.5 to 5 hours. According to the invention,
The fired conductive tin oxide powder is pulverized in an acid aqueous solution or an alkaline aqueous solution. The amount of powder added to the acid aqueous solution or alkaline aqueous solution is preferably 40 parts by weight or less per 60 parts by weight of the aqueous solution. If too much powder is added, it is difficult to apply acid or alkali to each individual powder evenly, making it difficult to form a sol, and even if sol formation is possible, the state cannot be maintained stably.
酸としては、硫酸、塩酸などのような鉱酸、酒
石酸、乳酸などのようなオキシカルボン酸、しゅ
う酸のようなカルボン酸を使用することができ、
アルカリとしては、水酸化ナトリウム、水酸化カ
リウムなどのようなアルカリ金属水酸化物、第四
級アンモニウム塩などが使用可能である。そし
て、酸又はアルカリの使用量は、処理すべき粉末
の少なくとも５重量％が適当であつて、これ以下
の使用量では焼成された導電性酸化錫の粉末をゾ
ル化することができない。酸又はアルカリの使用
量を増大させることは、本発明にとつて何ら不都
合をもたらさないが、経済的見地から余り推奨で
きない。 As acids, mineral acids such as sulfuric acid, hydrochloric acid, etc., oxycarboxylic acids such as tartaric acid, lactic acid, etc., carboxylic acids such as oxalic acid can be used,
As the alkali, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, quaternary ammonium salts, and the like can be used. The appropriate amount of acid or alkali to be used is at least 5% by weight of the powder to be treated; if the amount is less than this, the fired conductive tin oxide powder cannot be solified. Although increasing the amount of acid or alkali used does not bring any disadvantage to the present invention, it is not recommended from an economic standpoint.
粉砕処理に際しての温度は、30〜200℃の範囲
で任意に選択することができる。酸水溶液又はア
ルカリ水溶液の沸点以上の温度を採用する場合
は、溶液が液相を保持できるよう加圧されること
は勿論である。尚、処理温度を200℃以上に昇温
しても格別な有利な結果をもたらさない。焼成さ
れた導電性酸化錫の粉末をゾル化するに要する時
間は、添加した粉末の量及び粒径にもよるが、一
般に処理温度に関係し、処理温度が高ければ、短
い処理時間で粉末をゾル化することができる。 The temperature during the pulverization process can be arbitrarily selected within the range of 30 to 200°C. When a temperature higher than the boiling point of the acid aqueous solution or alkaline aqueous solution is employed, it goes without saying that the solution must be pressurized to maintain its liquid phase. Incidentally, even if the treatment temperature is increased to 200° C. or higher, no particularly advantageous results are brought about. The time required to solify the fired conductive tin oxide powder depends on the amount and particle size of the added powder, but it is generally related to the processing temperature; the higher the processing temperature, the shorter the processing time. Can be made into a sol.
本発明に係る方法においては、酸またはアルカ
リ水溶液に導電性酸化錫粉末を分散させると同時
に、分散液中の粉末を粉砕するための操作を行
う。この場合、分散液を攪拌するだけの単純な操
作で粉末を微細化し、ゾル化することもできる
が、例えばアトライター、サンドミル、ボールミ
ル等の適当な粉砕機を同時に使用することによ
り、粉末のゾル化を一層促進させることができ
る。また、酸またはアルカリ水溶液に分散する前
に、酸化錫の粉末を上記の粉砕機にて、予め粉砕
しておくことも、本発明によるゾル化を促進させ
る上で有効である。 In the method according to the present invention, conductive tin oxide powder is dispersed in an acid or alkaline aqueous solution, and at the same time, an operation for pulverizing the powder in the dispersion is performed. In this case, the powder can be made into a fine powder and sol by a simple operation of stirring the dispersion, but it is also possible to make the powder into a sol by simultaneously using an appropriate grinder such as an attritor, sand mill, or ball mill. It is possible to further promote the Furthermore, it is also effective to previously pulverize the tin oxide powder using the above-mentioned pulverizer before dispersing it in the acid or alkaline aqueous solution in promoting the sol formation according to the present invention.
上記した如く焼成された導電性酸化錫の粉末を
処理することによつて、酸水溶液又はアルカリ水
溶液を分散媒とし、導電性酸化錫がコロイド粒子
として分散する水性ゾルが調製される。この水性
ゾルは必要に応じて脱酸又は脱アルカリすること
も可能で、例えば脱アルカリにはイオン交換処理
を利用することができる。 By treating the conductive tin oxide powder calcined as described above, an aqueous sol in which conductive tin oxide is dispersed as colloidal particles is prepared using an acid aqueous solution or an alkaline aqueous solution as a dispersion medium. This aqueous sol can also be deoxidized or dealkalized as required; for example, ion exchange treatment can be used for dealkalization.
本発明のオルガノゾルは、前記した水性ゾルを
そのまま、もしくは脱酸又は脱アルカリした後、
その分散媒である水を親水性有機溶媒で置換する
方法によつて調製される。そして、その溶媒置換
法には公知の方法が利用でき、親水性有機溶媒と
しても、メタノール、エタノール、ｎ−プロパノ
ール、ｉ−プロパノール、ｎ−ブタノール、ｉ−
ブタノール、sec−ブタノール、tert−ブタノー
ル、エチレングリコール、トリメチレングリコー
ル、グリセリン等のアルコール類、メチルセロソ
ルブ、エチルセロソルブ、テトラヒドロフラン等
のエーテル類、メタノールアミン、エタノールア
ミン、モルホリン等のアミン類、ジメチルホルム
アミド、ｎ−メチル−２−ピロリドン等の酸アミ
ド類などが任意に使用可能である。 The organosol of the present invention can be prepared by using the above-mentioned aqueous sol as it is or after deoxidizing or dealkalizing the aqueous sol.
It is prepared by replacing water, the dispersion medium, with a hydrophilic organic solvent. Known methods can be used for the solvent substitution method, and hydrophilic organic solvents such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-
Alcohols such as butanol, sec-butanol, tert-butanol, ethylene glycol, trimethylene glycol, glycerin, ethers such as methyl cellosolve, ethyl cellosolve, tetrahydrofuran, amines such as methanolamine, ethanolamine, morpholine, dimethylformamide, Acid amides such as n-methyl-2-pyrrolidone can be optionally used.
［作用］
本発明の原料となる焼成された導電性酸化錫の
粉末を微視的に見た場合、この粉末は微細な一次
粒子の幾つかが焼成工程で焼結した焼結体の集合
と捉えることができるが、この粉末を酸水溶液又
はアルカリ水溶液中で粉砕処理すると、酸又はア
ルカリが個々の焼結体の焼結部分に作用してその
結合を解きほぐし、或いはその結合力を著しく低
下せしめるので、液を攪拌する程度の操作で焼成
された導電性酸化錫の粉末はコロイド次元まで微
細化されるものと考えられる。[Function] When looking microscopically at the fired conductive tin oxide powder that is the raw material of the present invention, it appears that some of the fine primary particles are a collection of sintered bodies sintered during the firing process. However, when this powder is pulverized in an acid aqueous solution or an alkali aqueous solution, the acid or alkali acts on the sintered parts of the individual sintered bodies, loosening their bonds or significantly reducing their bonding strength. Therefore, it is thought that the conductive tin oxide powder that is fired by an operation similar to stirring the liquid is refined to the colloidal level.
因に、本発明に係る導電性酸化錫のゾルは、従
来〔ゾル」と呼ばれてきたものと同様に、一年以
上安定であつて、分散粒子（コロイド粒子）の平
均粒径は0.1μ以下の範囲にあり、粒度分布は全粒
子の60％以上が粒径0.1μ以下の粒子で占められ
る。 Incidentally, the conductive tin oxide sol according to the present invention is stable for more than a year, similar to what has been conventionally called a sol, and the average particle size of the dispersed particles (colloidal particles) is 0.1μ. The particle size distribution is in the following range, with more than 60% of all particles being particles with a particle size of 0.1μ or less.
［実施例］
実施例 １
塩化錫57.7gと塩化アンチモン7.0gをメタノー
ル100gに溶かした溶液を調製した。90℃に加温
されて攪拌下にある水1000gに、前記の溶液を４
時間かけて添加して加水分解を行わせ、生成した
沈澱を濾別して洗浄し、乾燥空気中、500℃で２
時間焼成してアンチモンがドープした導電性酸化
錫の粉末（平均粒径2μ）を得た。[Examples] Example 1 A solution was prepared by dissolving 57.7 g of tin chloride and 7.0 g of antimony chloride in 100 g of methanol. Add 4 ml of the above solution to 1000 g of water heated to 90°C and stirred.
The precipitate was added over a period of time to cause hydrolysis, and the resulting precipitate was filtered and washed.
After firing for a period of time, antimony-doped conductive tin oxide powder (average particle size 2μ) was obtained.
この粉末30gを70gの水酸化カリウム水溶液
（KOH含量3.0g）に加え、この混合液を30℃に保
持しながらサンドミルで、３時間粉砕してゾルを
調製した。このゾルは沈澱物を含まず、固形分濃
度は30wt％であつて、分散粒子の平均粒径は
0.08μであつた。また、0.1μ以下の粒子の量は全
粒子の76％であつた。 30 g of this powder was added to 70 g of an aqueous potassium hydroxide solution (KOH content: 3.0 g), and the mixture was ground in a sand mill for 3 hours while maintaining the mixture at 30° C. to prepare a sol. This sol does not contain precipitates, has a solid content concentration of 30wt%, and has an average particle size of dispersed particles of
It was 0.08μ. In addition, the amount of particles of 0.1μ or less was 76% of the total particles.
尚、粉末及び分散粒子の平均粒径は、超遠心粒
度測定装置（堀場製作所製、商品名CAPA−500）
を用い、測定試料液中の固形分濃度を0.5wt％に
調整して、ゾルの場合は5000r.p.m.の遠心沈降
で、粉末の場合は自然沈降で測定した（以下同
じ）。 The average particle size of the powder and dispersed particles was measured using an ultracentrifugal particle size analyzer (manufactured by Horiba, trade name: CAPA-500).
The solid content concentration in the measurement sample liquid was adjusted to 0.5 wt%, and the sol was measured by centrifugal sedimentation at 5000 rpm, and the powder was measured by natural sedimentation (the same applies below).
実施例 ２
錫酸カリウム316.0gと吐酒石38.4gを686.0gの水
に溶かして溶液を調製した。50℃に加温されて攪
拌下にある1000gの水に、前記の溶液を硝酸と共
に12時間かけて添加し、系内のpHを8.5に保持し
て加水分解を行つてコロイド分散液を得た。この
分散液からコロイド粒子を濾別し、副生塩を洗浄
除去した後、ケーキを乾燥し、空気中350℃で３
時間焼成後、さらに空気中650℃で２時間焼成し
てアンチモンがドープした導電性酸化錫の粉末
（平均粒径40μ）を得た。Example 2 A solution was prepared by dissolving 316.0 g of potassium stannate and 38.4 g of tartarite in 686.0 g of water. The above solution was added to 1000 g of water heated to 50°C and stirred over 12 hours together with nitric acid, and the pH in the system was maintained at 8.5 to perform hydrolysis to obtain a colloidal dispersion. . After filtering the colloidal particles from this dispersion and washing off the by-product salts, the cake was dried and heated at 350°C in air for 30 minutes.
After firing for an hour, it was further fired in air at 650°C for 2 hours to obtain antimony-doped conductive tin oxide powder (average particle size 40μ).
この粉末30.0gを水酸化ナトリウム水溶液70g
（NaOH3.0g含有）に加え、この混合液を実施例
１と同様に処理してゾルを調製した。次いでこの
ゾルをイオン交換樹脂で処理することにより、脱
アルカリされたゾルを得た。このゾルは沈澱物を
含まず、固形分濃度は30wt％であつて、分散粒
子の平均粒径は0.07μであつた。そして、0.1μ以
下の粒子の量は全粒子の86％であつた。 30.0g of this powder and 70g of sodium hydroxide aqueous solution
(containing 3.0 g of NaOH), and this mixed solution was treated in the same manner as in Example 1 to prepare a sol. Next, this sol was treated with an ion exchange resin to obtain a dealkalized sol. This sol contained no precipitates, had a solid content concentration of 30 wt%, and had an average particle diameter of 0.07 μm. The amount of particles smaller than 0.1μ was 86% of the total particles.
実施例 ３
実施例２で得た粉末30gを70gのしゅう酸水溶
液（しゅう酸12.6g含有）に加え、この混合液を
この混合液を30℃に保持しながらサンドミルで３
時間粉砕した後、80℃で１時間保持してゾルを調
製した。このゾルは沈澱物を含まず、固形分濃度
は30wt％であつて、分散粒子の平均粒径は0.10μ
であつた。そして、0.1μ以下の粒子の量は全粒子
の63％であつた。Example 3 30g of the powder obtained in Example 2 was added to 70g of an oxalic acid aqueous solution (containing 12.6g of oxalic acid), and the mixture was heated in a sand mill for 3 minutes while maintaining the mixture at 30°C.
After grinding for an hour, the mixture was held at 80°C for 1 hour to prepare a sol. This sol does not contain precipitates, has a solid content concentration of 30wt%, and has an average particle size of 0.10μ.
It was hot. The amount of particles smaller than 0.1μ was 63% of the total particles.
実施例 ４
実施例２で得た粉末10gを水酸化ナトリウム水
溶液90g（NaOH1.0g含有）に加え、この混合液を
実施例１と同様に処理してゾルを調製した。この
ゾルは沈澱物を含まず、固形分濃度は10wt％で
あつて、分散粒子の平均粒径は0.10μであつた。
そして、0.1μ以下の粒子の量は全粒子の68％であ
つた。Example 4 10 g of the powder obtained in Example 2 was added to 90 g of an aqueous sodium hydroxide solution (containing 1.0 g of NaOH), and this mixed solution was treated in the same manner as in Example 1 to prepare a sol. This sol contained no precipitates, had a solid content concentration of 10 wt%, and had an average particle diameter of 0.10 μm.
The amount of particles smaller than 0.1μ was 68% of the total particles.
実施例 ５
実施例２で得た粉末30gを水酸化ナトリウム水
溶液70g（NaOH1.5g含有）に加え、この混合液を
実施例１と同様に処理してゾルを調製した。この
ゾルは沈澱物を含まず、固形分濃度は30wt％で
あつて、分散粒子の平均粒径は0.10μであつた。
そして、0.1μ以下の粒子の量は全粒子の61％であ
つた。Example 5 30 g of the powder obtained in Example 2 was added to 70 g of an aqueous sodium hydroxide solution (containing 1.5 g of NaOH), and the mixture was treated in the same manner as in Example 1 to prepare a sol. This sol contained no precipitates, had a solid content concentration of 30 wt%, and had an average particle diameter of 0.10 μm.
The amount of particles smaller than 0.1μ was 61% of the total particles.
実施例 ６
実施例２で得た粉末20gを水酸化カリウム水溶
液（KOH8.8g含有）80gに加え、この混合液を30
℃に保持しながらサンドミルで５時間粉砕してゾ
ルを調製した。このゾルは沈澱物を含まず、固形
分濃度は20wt％であつて、分散粒子の平均粒径
は0.03μであつた。そして、0.1μ以下の粒子の量
は全粒子の95％であつた。Example 6 20g of the powder obtained in Example 2 was added to 80g of potassium hydroxide aqueous solution (containing 8.8g of KOH), and the mixture was heated to 30g.
A sol was prepared by grinding with a sand mill for 5 hours while maintaining the temperature at °C. This sol contained no precipitates, had a solid content concentration of 20 wt%, and had an average particle diameter of 0.03 μm. The amount of particles of 0.1μ or less was 95% of all particles.
実施例 ７
実施例２で調製された脱アルカリゾルに、ｎ−
ブタノール300gを加え、ロータリーエバポレー
ターで水とｎ−ブタノールの一部を留去してｎ−
ブタノールを分散媒とするオルガノゾルを調製し
た。このゾルは沈澱物を含まず、固形分濃度は
30wt％であつて、分散粒子の平均粒径は0.07μで
あつた。そして、0.1μ以下の粒子の量は全粒子の
86％であつた。Example 7 The dealkalized sol prepared in Example 2 was treated with n-
Add 300 g of butanol and distill off water and part of n-butanol using a rotary evaporator to remove n-butanol.
An organosol using butanol as a dispersion medium was prepared. This sol does not contain precipitates, and the solids concentration is
It was 30wt%, and the average particle size of the dispersed particles was 0.07μ. And the amount of particles smaller than 0.1μ is the total amount of particles.
It was 86%.
比較例
実施例２で得られた粉末30gを70gの水酸化ナ
トリウム水溶液で処理するに際し、この水溶液に
含まれるNaOHの量を0.7に減少させた以外は実
施例５と同様に粉末を処理したが、ゾルを得るこ
とはできず、得られたものは沈澱が存在する分散
液であつた。尚、分散粒子の平均粒径は0.20μで
あり、0.1μ以下の粒子の量は全粒子の26％であつ
た。Comparative Example When treating 30 g of the powder obtained in Example 2 with 70 g of an aqueous sodium hydroxide solution, the powder was treated in the same manner as in Example 5, except that the amount of NaOH contained in this aqueous solution was reduced to 0.7. However, it was not possible to obtain a sol, and what was obtained was a dispersion containing a precipitate. The average particle diameter of the dispersed particles was 0.20μ, and the amount of particles smaller than 0.1μ was 26% of the total particles.
［発明の効果］
本発明に係るゾルは、導電性酸化錫のコロイド
粒子が水又は親水性有機溶媒に分散した極めて安
定な（室温で１年以上安定）ものであるので、各
種の用途に用いることができる。例えば、透明塗
料にこのゾルを配合すれば、塗料中でコロイド粒
子が凝集してしまうことがなく、ゾル中の粒径を
保持したまま容易に分散する。そして、この塗料
をガラス、プラスチツク等の透明基材に塗布する
ことで、基材の透明性を損なうことなく高導電性
の透明被膜を、基材表面に形成させることができ
る。[Effects of the Invention] The sol according to the present invention is extremely stable (stable for more than one year at room temperature) in which colloidal particles of conductive tin oxide are dispersed in water or a hydrophilic organic solvent, so it can be used for various purposes. be able to. For example, if this sol is blended into a transparent paint, the colloidal particles will not aggregate in the paint and will be easily dispersed while maintaining the particle size in the sol. By applying this paint to a transparent substrate such as glass or plastic, a highly conductive transparent film can be formed on the surface of the substrate without impairing the transparency of the substrate.
Claims (1)
化錫粉末を酸水溶液又はアルカリ水溶液中で粉砕
処理して得られた粒子がコロイド粒子として水又
は親水性有機溶媒に分散したゾル。 ２ 水又は親水性有機溶媒に分散した粒子の量が
40.0重量％以下である特許請求の範囲第１項記載
のゾル。 ３ 焼成された、異種元素をドープした導電性酸
化錫粉末を、酸水溶液又はアルカリ水溶液中で粉
砕処理することからなる、異種元素をドープした
導電性酸化錫がコロイド粒子として水に分散した
水性ゾルの製造方法。 ４ 焼成された、異種元素をドープした導電性酸
化錫粉末を、酸水溶液又はアルカリ水溶液中で粉
砕処理して異種元素をドープした導電性酸化錫が
コロイド粒子として水に分散した水性ゾルを調製
し、しかる後この水性ゾルの分散媒を親水性有機
溶媒で溶媒置換することからなる、異種元素をド
ープした導電性酸化錫がコロイド粒子として親水
性有機溶媒に分散したオルガノゾルの製造方法。[Claims] 1. Particles obtained by pulverizing calcined conductive tin oxide powder doped with a different element in an acid aqueous solution or an alkaline aqueous solution are dispersed in water or a hydrophilic organic solvent as colloidal particles. Sol. 2 The amount of particles dispersed in water or hydrophilic organic solvent is
The sol according to claim 1, which has a content of 40.0% by weight or less. 3. An aqueous sol in which conductive tin oxide doped with a different element is dispersed in water as colloidal particles, which is obtained by pulverizing fired conductive tin oxide powder doped with a different element in an aqueous acid solution or aqueous alkali solution. manufacturing method. 4. The calcined conductive tin oxide powder doped with a different element is pulverized in an acid aqueous solution or an alkaline aqueous solution to prepare an aqueous sol in which the conductive tin oxide doped with a different element is dispersed in water as colloidal particles. A method for producing an organosol in which conductive tin oxide doped with a different element is dispersed as colloidal particles in a hydrophilic organic solvent, the method comprising subsequently replacing the dispersion medium of this aqueous sol with a hydrophilic organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7528386A JPS62230617A (en) | 1986-04-01 | 1986-04-01 | Tin oxide sol and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7528386A JPS62230617A (en) | 1986-04-01 | 1986-04-01 | Tin oxide sol and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62230617A JPS62230617A (en) | 1987-10-09 |
| JPH0587445B2 true JPH0587445B2 (en) | 1993-12-16 |
Family
ID=13571743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7528386A Granted JPS62230617A (en) | 1986-04-01 | 1986-04-01 | Tin oxide sol and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62230617A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002145614A (en) * | 2000-11-08 | 2002-05-22 | Taki Chem Co Ltd | Titanium oxide sol composition |
| JP2003095657A (en) * | 2001-09-25 | 2003-04-03 | Taki Chem Co Ltd | Titanium oxide sol dispersed in organic solvent and method of manufacturing it |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2759470B2 (en) * | 1988-12-22 | 1998-05-28 | 富士チタン工業株式会社 | Stannate sol and method for producing the same |
| NL9000268A (en) * | 1990-02-05 | 1991-09-02 | Oce Nederland Bv | Doped tin oxide powder, a process for its preparation, and its use in electrically conductive or anti-static coatings. |
| KR960002743B1 (en) * | 1990-11-21 | 1996-02-26 | 쇼꾸바이 가세이 고오교 가부시끼가이샤 | Coating solution for forming transparent conductive coating and the process for preparing the same |
| JP2003073122A (en) * | 2001-09-04 | 2003-03-12 | Mitsui Chemicals Inc | Inorganic microparticle dispersion and composite material composition produced by using the same |
| US20070297966A1 (en) | 2006-06-22 | 2007-12-27 | Nissan Chemical Industries, Ltd. | Conductive tin oxide sol and process for producing same |
| JP4877518B2 (en) * | 2006-06-22 | 2012-02-15 | 日産化学工業株式会社 | Conductive tin oxide sol and method for producing the same |
| CN110504362B (en) * | 2019-07-17 | 2023-06-16 | 浙江浙能技术研究院有限公司 | SnO (tin oxide) 2 Modification method of electron selective transport layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62207717A (en) * | 1986-03-06 | 1987-09-12 | Taki Chem Co Ltd | Sol of crystalline tin oxide and its preparation |
-
1986
- 1986-04-01 JP JP7528386A patent/JPS62230617A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62207717A (en) * | 1986-03-06 | 1987-09-12 | Taki Chem Co Ltd | Sol of crystalline tin oxide and its preparation |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002145614A (en) * | 2000-11-08 | 2002-05-22 | Taki Chem Co Ltd | Titanium oxide sol composition |
| JP2003095657A (en) * | 2001-09-25 | 2003-04-03 | Taki Chem Co Ltd | Titanium oxide sol dispersed in organic solvent and method of manufacturing it |
| JP4521801B2 (en) * | 2001-09-25 | 2010-08-11 | 多木化学株式会社 | Organic solvent-dispersed titanium oxide sol and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62230617A (en) | 1987-10-09 |
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