JPS6144709A - Production of hydrous silicic acid having conductivity - Google Patents
Production of hydrous silicic acid having conductivityInfo
- Publication number
- JPS6144709A JPS6144709A JP16487684A JP16487684A JPS6144709A JP S6144709 A JPS6144709 A JP S6144709A JP 16487684 A JP16487684 A JP 16487684A JP 16487684 A JP16487684 A JP 16487684A JP S6144709 A JPS6144709 A JP S6144709A
- Authority
- JP
- Japan
- Prior art keywords
- water
- silicic acid
- compound
- tin
- manufacturing
- 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.)
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- Silicon Compounds (AREA)
Abstract
Description
本発明は、導電性を有する含水珪酸の製造方法に関し、
特に高温下で着色しない白色の導電性含水珪酸を簡便に
製造する方法を提供するものである。
従来より含水珪酸は天然ゴム、合成ゴムの充填剤、各種
合成樹脂の不透明及びブロッキング防止剤、紙の填料、
ペイント配合剤、農薬吸着担体、粘度調節剤などとして
広い分野に使用されている。
近年、特に上記の如きゴム、合成樹脂、塗料、紙などに
導電性を付与するために、導電性を有する含水珪酸が要
望されている。しかしながら、含水珪酸は一般に電′気
絶縁体であり、導電性を有していない。そのため、例え
ば特開昭５．６−１１４２１５〜１１４２１８号には、
酸化チタンなど白色金属酸化物粉末に酸化錫、またはア
ンチモンと錫化合物を被覆してなる白色導電性複合粉末
及びその製造方法が提案されている。すなわち、これら
の製造方法は、白色金属酸化物粉末の懸濁液に塩化錫、
または塩化アンチモンと塩化錫のアルコール溶液を添加
して処理する方法である。これに対して、本発明者等は
、導電性を良好かつ安定して有する含水珪酸を得るため
に、珪酸アルカリを酸で中和して含水珪酸を製造するに
際して、反応系に錫化合物または錫化合物とアンチモン
化合物とを存在させる方法を提案した。（特願昭５８−
６３７５６号）
本発明者等は、さらに導電性を有する珪酸の製造方法に
ついて鋭意研究を進めた結果、珪酸アルカリを錫化合物
及び水溶性錫化合物と反応させるこにによって、極めて
良好の導電性を有し、且つ高温において着色しない白色
の含水珪酸が得られることを見出し、本発明を提供する
に至った。
すなわち、本発明は珪酸アルカリと錫化合物及び水溶性
弗素化合物を含む溶液を反応させることを特徴とする導
電性を有する含水珪酸の製造方法で−ある。
本発明によれば珪酸アルカリと錫化合物及び水溶性弗素
化合物とを反応させるため生成する含水珪酸と同時に該
珪酸に弗素をトープした酸化錫が均一に含有されて析出
する。したがって、本発明により得られる含水珪酸は該
含水珪酸の表面および内部に弗素をドープした酸化錫が
強固に含有されるため、高温において着色しないで且つ
所望の導電性を安定して発揮することができるものと推
測される。
本発明において珪酸アルカリと錫化合物及び水溶性弗素
化合物を反応させる方法は特に制限なく用いられる。一
般には、珪酸アルカリ水溶液を昇温し、該水溶液中に水
溶性錫化合物と水溶性弗素化合物を含む水溶液を添加し
てＰＨ調整を行い、珪酸アルカリ粒子を完全に析出せし
め午後、濾過水洗、乾燥、必要により粉砕し、該粉砕品
を温度５００〜９００℃で焼成する方法が推奨される。
本発明の珪酸アルカリとしては、例えば珪酸ナトリウム
、珪酸カリウム、珪酸リチウム、珪酸アンモニウムなと
であり、これらが一般に水溶液として使用され、特に珪
酸ナトリウム（ソーダ）の水溶液が工業的に使用される
。珪酸ナトリウム（Ｎ ａ２０ φＳ ｉ ０７）のＳ
ｉＯ２とＮ ａ２ｏのモル比（Ｓｉ ０２／ Ｎ ＪＯ
）は］、Ｆｉ〜２．５が好ましく、該モル比が１．５以
下の場合はアルカリが多くなるため経済的でなく、また
、モル比が２．５以上になるとシリカへの錫化合物の担
持量が減少するため導電性の良好なシリカが得られない
。
本発明の含水珪酸に所望の導電性を付与するためには、
前述した珪酸アルカリ水溶液にアルコールを添加するこ
とが好ましい。アルコールの添加量は珪酸アルカリ水溶
液中にアルコールの容積割合が１０％以下で存在させる
ことが好ましく、１０％以上になると珪酸アルカリとア
ルコールのエステル化が起こり、ゲル化物が生じるため
撹拌が困難となる。アルコールとしては、メチルアルコ
ール、エチルアルコール、イソプロピルアルコール等が
好ましく用いられる。
本発明において錫化合物及び水溶性弗素化合物は、一般
に、水、アルコールなどの溶媒に溶解して用いることが
、得られる含水珪酸に所望の導電性を安定かつ均一に付
与するために好ましい。したがって、錫化合物及び水溶
性弗素化合物としては溶媒に可溶性であればよく、例え
ば錫化合物としては塩化錫が一般に用いられ、そのほか
硫酸塩、酸化物なども適宜用いられる。また、水溶性弗
素化合物としては弗化アンモニウムが好ましく用いられ
る。また本発明の含水珪酸に所望の導電性を付与するた
めには、珪酸アルカリ溶液において、錫化合物をＮａＯ
に対して重量比で１．６〜２゜２で存在させることが好
ましい。すなわち、錫化合物が一ヒ記１．６より少ない
場合には、酸化錫の析出が不充分であるため含水珪酸に
所望の導電性を充分に付与できず、また２、２より多く
しても、導電性の付与に一段の向上は認められない。一
方、水溶性弗素化合物は、錫化合物（重量）に対し３７
８（重量）％の割合で存在させることが好ましい。すな
わち、水溶性弗素化合物が上記３（重１１：）％より少
ない場合には、酸化錫中の弗素のドープ量が少ないため
得られる含水珪酸に、所望の導電性を充分に付与できず
、また８（重り１％より多くしても、導電性の付与に一
段の向上が認められない。
上記した珪酸アルカリに錫化合物及び水溶性弗素化合物
を添加して珪酸ゾルを生成する反応は、仕込み珪酸アル
カリの濃度、温度、反応終了時のＰＨ１撹拌などの影響
が大きい。すなわち、仕込み珪酸アルカリの濃度が高い
場合にはゲル化し、撹拌が困難となるため、一般に５ｔ
０２として２〜１０ ｇ ／ ］０００ｍ１とすること
が好ましい。上記５１０２が２ ｇ ／ １００ｍ１以
下では経済的でないばかりでなく、珪酸ゲルの生成が困
難となる。温度は一般に４０〜１００℃が好ましく、４
０℃より低い場合には反応液の粘度が高くなり、得られ
る含水珪酸の比表面積に影響するため適宜調節すればよ
い。
反応終了後のＰＨは導電性に影響し、ＰＨが７以下にな
ると導電性は低下する。撹拌は反応が局部的に起こらな
いように、充分に効かずことが望ましい。
反応終了後の珪酸スラリーは、常法により濾過水洗して
副生塩を除去した後、乾燥、粉砕、分級する。さらに必
要により、この含水珪酸を電気炉で５００〜７００℃の
温度で１〜２時間焼成することにより、所望の導電性を
有する含水珪酸を得ることができる。焼成方法は公知の
方法が特に制限なくもちいられるが、電気炉又は瞬間的
に火焔と接触させる方法が好ましく用いられる。
本発明は上記した含水珪酸の製造方法において、珪酸ア
ルカリと錫化合物及び水溶性弗素化合物を反応させるこ
とによって良好な導電性を有する微細な含水珪酸を得る
ことかだきる。かくして得られた本発明の導電性を有す
る含水珪酸は、例えば、通電感熱紙、静電記録紙、静電
塗料、帯電防止用プラスチックやゴム材などの充填剤と
して極めて有用である。
以下、実施例を挙げるが、本発明はこれらに制限される
ものではない。なお、°実施例及び比較例における測定
方法を示す。
（１）比抵抗（Ω・ｃｍ）
ブリッヂ回路（横河電機製）で測定
（２）白色度
Ｋ ｅ ｆ、ｔ、光電白度計（にｅ ｔ、ｔ、科学研究
新製）実施例１
ＳｉＯｉｌ）１度４４．４１％およびＮ ａ２０５度２
１゜６５％の珪ｍソーダ溶液５４ｏ１、水２２２０ｍ１
、エタノール２４０ｍ１を、容積５？λの内部加熱式反
応器に仕込み、液温度を６０度とした。
次に水６００ｍ１に塩化錫（ＳｎＣＩ）２１０ｇとフッ
化アンモニウム１２．６ｇを溶解した混合液を９０分で
反応槽へ添加し、添加終了後、反応温度を９０℃とし、
この状態で２０分熟成し、溶液のＰＨを９．１０とThe present invention relates to a method for producing hydrated silicic acid having conductivity,
The object of the present invention is to provide a method for easily producing white conductive hydrated silicic acid that does not discolor especially at high temperatures. Hydrous silicic acid has traditionally been used as a filler for natural rubber and synthetic rubber, as an opaque and anti-blocking agent for various synthetic resins, as a filler for paper,
It is used in a wide range of fields such as paint compounding agents, pesticide adsorption carriers, and viscosity modifiers. In recent years, there has been a demand for hydrated silicic acid having electrical conductivity, particularly in order to impart electrical conductivity to rubber, synthetic resins, paints, paper, etc. as mentioned above. However, hydrated silicic acid is generally an electrical insulator and has no electrical conductivity. Therefore, for example, in JP-A-5.6-114215 to 114218,
BACKGROUND ART A white conductive composite powder in which a white metal oxide powder such as titanium oxide is coated with tin oxide or an antimony and tin compound, and a method for producing the same have been proposed. That is, these manufacturing methods involve adding tin chloride,
Another method is to add an alcoholic solution of antimony chloride and tin chloride. On the other hand, in order to obtain hydrated silicic acid having good and stable conductivity, the present inventors added a tin compound or a tin compound to the reaction system when producing hydrated silicic acid by neutralizing alkali silicate with acid. A method was proposed in which a compound and an antimony compound were made to exist. (Special application 1982-
63756) As a result of further intensive research into a method for producing silicic acid with electrical conductivity, the present inventors have discovered that it has extremely good electrical conductivity by reacting an alkali silicate with a tin compound and a water-soluble tin compound. However, the present inventors have discovered that a white hydrated silicic acid that is not colored at high temperatures can be obtained, and the present invention has been provided. That is, the present invention is a method for producing hydrated silicic acid having electrical conductivity, which is characterized by reacting an alkali silicate with a solution containing a tin compound and a water-soluble fluorine compound. According to the present invention, since an alkali silicate is reacted with a tin compound and a water-soluble fluorine compound, tin oxide, which is a silicic acid doped with fluorine, is uniformly contained and precipitated at the same time as the hydrous silicic acid produced. Therefore, since the hydrated silicic acid obtained by the present invention strongly contains fluorine-doped tin oxide on the surface and inside of the hydrated silicic acid, it is not colored at high temperatures and can stably exhibit the desired conductivity. It is assumed that it is possible. In the present invention, the method of reacting an alkali silicate with a tin compound and a water-soluble fluorine compound can be used without particular limitation. Generally, the temperature of an aqueous alkali silicate solution is raised, and an aqueous solution containing a water-soluble tin compound and a water-soluble fluorine compound is added to the aqueous solution to adjust the pH, and the alkali silicate particles are completely precipitated.In the afternoon, the particles are filtered, washed with water, and dried. A recommended method is to pulverize the material if necessary, and then sinter the pulverized product at a temperature of 500 to 900°C. Examples of the alkali silicate of the present invention include sodium silicate, potassium silicate, lithium silicate, and ammonium silicate, which are generally used as an aqueous solution, and in particular, an aqueous solution of sodium silicate (soda) is used industrially. S of sodium silicate (N a20 φS i 07)
Molar ratio of iO2 and Na2o (Si02/N JO
) is preferably Fi ~ 2.5; if the molar ratio is less than 1.5, the amount of alkali increases, making it uneconomical, and if the molar ratio is more than 2.5, the tin compound may not be absorbed into the silica. Silica with good conductivity cannot be obtained because the amount supported is reduced. In order to impart desired conductivity to the hydrated silicic acid of the present invention,
It is preferable to add alcohol to the aqueous alkali silicate solution mentioned above. Regarding the amount of alcohol added, it is preferable that the volume ratio of alcohol be present in the aqueous alkali silicate solution at 10% or less. If it exceeds 10%, esterification of the alkali silicate and alcohol will occur, resulting in a gelled product, making stirring difficult. . As the alcohol, methyl alcohol, ethyl alcohol, isopropyl alcohol, etc. are preferably used. In the present invention, the tin compound and the water-soluble fluorine compound are generally preferably used after being dissolved in a solvent such as water or alcohol in order to stably and uniformly impart the desired conductivity to the resulting hydrated silicic acid. Therefore, the tin compound and the water-soluble fluorine compound need only be soluble in the solvent. For example, tin chloride is generally used as the tin compound, and sulfates, oxides, and the like may also be used as appropriate. Moreover, ammonium fluoride is preferably used as the water-soluble fluorine compound. In addition, in order to impart desired conductivity to the hydrated silicic acid of the present invention, it is necessary to add a tin compound to NaO in the alkaline silicate solution.
It is preferable that the amount is present in a weight ratio of 1.6 to 2°2. That is, if the amount of tin compound is less than 1.6, the precipitation of tin oxide is insufficient and the desired conductivity cannot be imparted to the hydrated silicic acid, and even if the amount is more than 2. , no further improvement in conductivity was observed. On the other hand, the water-soluble fluorine compound is 37% compared to the tin compound (weight).
Preferably, it is present in a proportion of 8% (by weight). That is, if the amount of the water-soluble fluorine compound is less than the above 3 (11% by weight), the desired conductivity cannot be sufficiently imparted to the obtained hydrated silicic acid because the amount of fluorine doped in tin oxide is small. 8 (Even if the weight is increased to more than 1%, no further improvement in imparting conductivity is observed. The reaction of adding a tin compound and a water-soluble fluorine compound to the above-mentioned alkali silicate to produce a silicic acid sol is a The influence of alkali concentration, temperature, PH1 stirring at the end of the reaction, etc. is large.In other words, if the concentration of the charged alkali silicate is high, it will gel and stirring will be difficult, so generally 5t
02 is preferably 2 to 10 g/]000ml. If the amount of 5102 is less than 2 g/100 m1, it is not only uneconomical but also difficult to produce silicic acid gel. The temperature is generally preferably 40 to 100°C, and 4
If the temperature is lower than 0°C, the viscosity of the reaction liquid becomes high, which affects the specific surface area of the obtained hydrous silicic acid, so it may be adjusted as appropriate. The pH after the reaction is completed affects the conductivity, and when the pH becomes 7 or less, the conductivity decreases. It is desirable that the stirring is not sufficiently effective so that the reaction does not occur locally. After the completion of the reaction, the silicic acid slurry is filtered and washed with water to remove by-product salts, followed by drying, pulverization, and classification. Furthermore, if necessary, the hydrated silicic acid having desired conductivity can be obtained by firing the hydrated silicic acid in an electric furnace at a temperature of 500 to 700° C. for 1 to 2 hours. As the firing method, any known method may be used without particular limitation, but an electric furnace or a method of instantaneous contact with flame is preferably used. In the method for producing hydrated silicic acid described above, the present invention enables to obtain fine hydrated silicic acid having good conductivity by reacting an alkali silicate with a tin compound and a water-soluble fluorine compound. The conductive hydrated silicic acid of the present invention thus obtained is extremely useful as a filler for, for example, electrically conductive thermal paper, electrostatic recording paper, electrostatic paint, antistatic plastics, rubber materials, and the like. Examples are given below, but the present invention is not limited thereto. In addition, measurement methods in Examples and Comparative Examples are shown below. (1) Specific resistance (Ω・cm) Measured with a bridge circuit (manufactured by Yokogawa Electric) (2) Whiteness K e f, t, photoelectric whiteness meter (ni e t, t, manufactured by Kagaku Kenkyushin) Example 1 SiOil) 1 degree 44.41% and Na 205 degree 2
1°65% silica soda solution 54o1, water 2220ml
, 240ml of ethanol, volume 5? The mixture was charged into a λ internally heated reactor, and the liquid temperature was set at 60 degrees. Next, a mixture of 210 g of tin chloride (SnCI) and 12.6 g of ammonium fluoride dissolved in 600 ml of water was added to the reaction tank over 90 minutes, and after the addition was completed, the reaction temperature was set to 90°C.
Aged in this state for 20 minutes, and the pH of the solution was adjusted to 9.10.
【ノ
た。得られたスラリー溶液を濾過、水洗して得たケーク
を１１０℃で乾燥して含水珪酸を得た。次いで、粉砕、
分級し、電気炉中で６５０℃で６０分焼成して、比抵抗
および白色度の測定に供した。その含水珪酸についての
測定値を第１表に示す。
実施例２
実施例Ｉにおいて、珪酸ソーダ溶液２７０ｍ１、水２４
８４ｍ１、エタノール２４６１、塩化錫１１７ｇ１フツ
化アンモニウム７．０ｇにしたほかは同様に製造した。
その結果を第１表に示す。
実施例３
実施例】において、Ｓ ｉ ０２ｉＰ！ａ ４４ 、６
３ ％ 及びＮａ２０ｍ度２２．２４％の珪酸ソーダ溶
液５３８ｍ１、水２２１６ｍ１、エタノール２４６ｍ１
、塩化錫２４０ｇ、フッ化アンモニウム１４．４ｇにし
たほかは、同様に製造した。その結果を第１表に示す。
実施例４
実施例１において、エタノールは使用せず、水２４６０
ｍ１にしたほかは、同様に製造した。その結果を第１表
に示す。
比較例Ｉ
Ｓ ｒ ｏＪ度２７．０９％およびＮａ２Ｏ濃度９゜２
４％の珪酸ソーダ溶液１０３４ｍ１、水１７６７ｍ１を
容積５１！にの内部加熱式反応器に仕込み、液温度６０
℃とした。
次に、水７００１に塩化錫（ＳｎＣＩ４）１９６ｇを溶
解し、これを９０分で反応槽へ添加し、この状態で６０
分保持し熟成し、溶液のＰＨを７゜３８しとた。得られ
たスラリー溶液を濾過・水洗して得たケークを１１０℃
で乾燥して含水珪酸を得た。次いで粉砕・分級し、６５
０℃の電気炉中で６０分焼成して、比抵抗及び白色度の
測定に供した。その結果を第１表に示す。
千−続補正書
昭和５９年８月２１日
特許庁長官 志 賀 学 殿
２、発明の名称 導電性を有する含水珪酸の製造ブ
ｊ’を去３、補正をする渚
事件との関係 特許出願人
住 所 山口県徳山市御影町１番１号６、補正の対
象 明細層の発明の詳細な説明ｏ：＋ ４１１１７
、補正の内容
（１） 明細冑第６真下から２行目のｒＮａＯＪをｒ
Ｎ ａ、ｏ Ｊに訂１１：する。
（２） 同第９頁下から４行目のｒｓｎｃｌＪを（３
） 同第１２頁第１表の比抵抗
ｒ７．６Ｘ１０Ｊをｒ７．６Ｘ１０’Ｊｒ７．３Ｘ１０
Ｊを「７．３×１ｏ４１ｒ１．８Ｘ１０Ｊを「１．８×
１０ｊＥ」ｒｌ、 ３Ｘ１０Ｊ ｔｉ ｒｌ、 ３Ｘ１
０Ｇ１ｒ１．８Ｘ１０Ｊを「１．８Ｘ１０′７１へ、夫
々訂正する。
以上[Nota. The obtained slurry solution was filtered and washed with water, and the resulting cake was dried at 110° C. to obtain hydrated silicic acid. Then, crushing,
It was classified and fired at 650° C. for 60 minutes in an electric furnace, and then subjected to measurement of specific resistance and whiteness. Table 1 shows the measured values for the hydrated silicic acid. Example 2 In Example I, 270 ml of sodium silicate solution, 24 ml of water
It was produced in the same manner except that 84 ml, ethanol 2461, tin chloride 117 g and ammonium fluoride 7.0 g were used. The results are shown in Table 1. Example 3 In Example, S i 02iP! a 44, 6
3% and 20m Na 22.24% sodium silicate solution 538ml, water 2216ml, ethanol 246ml
, was produced in the same manner except that 240 g of tin chloride and 14.4 g of ammonium fluoride were used. The results are shown in Table 1. Example 4 In Example 1, ethanol was not used and water 2460
It was manufactured in the same manner except that the size was changed to m1. The results are shown in Table 1. Comparative Example I S r o J degree 27.09% and Na2O concentration 9°2
1034ml of 4% sodium silicate solution and 1767ml of water in a volume of 51! Pour into an internally heated reactor and bring the liquid temperature to 60
℃. Next, 196 g of tin chloride (SnCI4) was dissolved in 7001 of water, and this was added to the reaction tank over 90 minutes.
The pH of the solution was adjusted to 7.38. The resulting slurry solution was filtered and washed with water, and the resulting cake was heated to 110°C.
was dried to obtain hydrated silicic acid. Next, it is crushed and classified, and 65
It was fired for 60 minutes in an electric furnace at 0° C. and used for measurement of specific resistance and whiteness. The results are shown in Table 1. 1,000-Continued Amendment August 21, 1980 Manabu Shiga, Commissioner of the Patent Office2, Title of Invention: Manufacturing of conductive hydrated silicic acid 3, amended Relationship with the Nagisa Case Patent Applicant Address: 1-1-6, Mikage-cho, Tokuyama-shi, Yamaguchi Prefecture; Subject of amendment: Detailed description of the invention of detailed layer o: + 41117
, Contents of correction (1) rNaOJ on the second line from the bottom of No. 6 of the specification
N a, o J to revise 11:. (2) Change rsnclJ in the fourth line from the bottom of page 9 to (3
) The specific resistance r7.6X10J in Table 1 on page 12 of the same page is r7.6X10'Jr7.3X10
J to “7.3×1o41r1.8X10J” to “1.8×
10jE”rl, 3X10J ti rl, 3X1
Correct 0G1r1.8X10J to 1.8X10'71.
Claims (11)
含む溶液を反応させることを特徴とする導電性を有する
含水珪酸の製造方法。(1) A method for producing hydrated silicic acid having electrical conductivity, which comprises reacting an alkali silicate with a solution containing a tin compound and a water-soluble fluorine compound.
範囲第１項記載の製造方法。(2) The manufacturing method according to claim 1, wherein the alkali silicate is sodium silicate.
比（ＳｉＯ＿２／Ｎａ＿２Ｏ）が１．５〜２．５である
特許請求の範囲第２項記載の製造方法。(3) The manufacturing method according to claim 2, wherein the molar ratio of SiO_2 and Na_2O (SiO_2/Na_2O) of sodium silicate is 1.5 to 2.5.
請求の範囲第１項記載の製造方法。(4) The manufacturing method according to claim 1, which is an aqueous alkali silicate solution containing alcohol.
１０％以下である特許請求の範囲第４項記載の製造方法
。(5) The manufacturing method according to claim 4, wherein the volume ratio of alcohol in the aqueous alkali silicate solution is 10% or less.
性錫化合物を含む混合溶液を添加する特許請求の範囲第
１項記載の製造方法。(6) The manufacturing method according to claim 1, wherein a mixed solution containing a water-soluble fluorine compound and a water-soluble tin compound is added to the alkaline silicate solution.
載の製造方法。(7) The manufacturing method according to claim 1, wherein the tin compound is tin chloride.
比で１．６〜２．０添加する特許請求の範囲第１項記載
の製造方法。(8) The manufacturing method according to claim 1, wherein the tin compound is added in a weight ratio of 1.6 to 2.0 to the alkali silicate.
請求の範囲第１項記載の製造方法。(9) The manufacturing method according to claim 1, wherein the water-soluble fluorine compound is ammonium fluoride.
量％添加する特許請求の範囲第１項記載の製造方法。(10) The manufacturing method according to claim 1, wherein 3 to 8% by weight of a water-soluble fluorine compound is added to the tin compound.
請求の範囲第１項記載の製造方法。(11) The manufacturing method according to claim 1, wherein the reaction product is calcined at 500 to 900°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16487684A JPS6144709A (en) | 1984-08-08 | 1984-08-08 | Production of hydrous silicic acid having conductivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16487684A JPS6144709A (en) | 1984-08-08 | 1984-08-08 | Production of hydrous silicic acid having conductivity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6144709A true JPS6144709A (en) | 1986-03-04 |
| JPH0455967B2 JPH0455967B2 (en) | 1992-09-07 |
Family
ID=15801592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16487684A Granted JPS6144709A (en) | 1984-08-08 | 1984-08-08 | Production of hydrous silicic acid having conductivity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6144709A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0532459U (en) * | 1991-10-15 | 1993-04-27 | 積水化成品工業株式会社 | Antifreeze water pipe |
| EP0984035A4 (en) * | 1997-05-21 | 2001-11-07 | Otsuka Chemical Co Ltd | Rubber composition |
-
1984
- 1984-08-08 JP JP16487684A patent/JPS6144709A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0532459U (en) * | 1991-10-15 | 1993-04-27 | 積水化成品工業株式会社 | Antifreeze water pipe |
| EP0984035A4 (en) * | 1997-05-21 | 2001-11-07 | Otsuka Chemical Co Ltd | Rubber composition |
| US6479582B1 (en) | 1997-05-21 | 2002-11-12 | Otsuka Chemical Co., Ltd. | Rubber composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0455967B2 (en) | 1992-09-07 |
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