JP2012118032A - Quantitative analysis method of higher fatty acid contained in inorganic powder - Google Patents
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Description
本発明は、セラミックス、導電性ペースト、銀電池等に使用される酸化銀粉等の無機粉体に含有される高級脂肪酸の定量分析方法に関する。 The present invention relates to a method for quantitative analysis of higher fatty acids contained in inorganic powders such as silver oxide powders used in ceramics, conductive pastes, silver batteries and the like.
無機材の粉体である無機粉体は、産業上さまざまな用途において用いられている。無機粉体そのものも市場において流通される製品であるが、無機粉体を原料として成形品を製造するセラミックス製品、磁石製品、電池などがある。これらは、多種の機能別の粉体を混合してなる製品が殆どである。 Inorganic powders, which are inorganic powders, are used in various industrial applications. Inorganic powders themselves are products that are distributed in the market, but there are ceramic products, magnet products, batteries, etc. that manufacture molded products using inorganic powders as raw materials. Most of these products are made by mixing various types of powders according to function.
無機粉体は、何らかの有機物を表面処理剤として被覆されている。これは、表面処理剤によって無機粉体同士の固着を防止し分散性を高める目的や、無機粉体と他の樹脂などの材料との混合の際に、当該混合をし易くすることが目的である。
これらの有機物の表面処理剤の種類は他種多様であり、無機粉体の性状、使用目的用途によって設計・選択されている。
そして無機粉体の分散等を改善する表面処理剤として高級脂肪酸があり、様々な用途に用いられている。高級脂肪酸としては、ステアリン酸、オレイン酸、リノール酸などが代表的である。
The inorganic powder is coated with some organic substance as a surface treatment agent. This is for the purpose of preventing the adhesion between inorganic powders by the surface treatment agent and improving the dispersibility, and for the purpose of facilitating the mixing when mixing the inorganic powder and other resin materials. is there.
There are various types of surface treatment agents for these organic substances, and they are designed and selected according to the properties of inorganic powder and intended use.
Higher fatty acids are used as surface treatment agents for improving the dispersion of inorganic powders and are used in various applications. As the higher fatty acid, stearic acid, oleic acid, linoleic acid and the like are typical.
高級脂肪酸は、上述した表面処理剤以外の目的にも用いられる場合がある。一方、無機粉体に所望特性を発揮させる為、複数の高級脂肪酸の混合や、高級脂肪酸と糖類、アルコール、有機酸とを混合する多種混合も用いられている。無機粉体において所望特性を得る為に、高級脂肪酸を始めとして用いられる有機物は、種類、量とも重要な管理項目として製造工程において管理されている。従って、無機粉体を始めとする各種製品に含まれる高級脂肪酸を始めとした有機物の量を定量することは、品質管理においては重要な事項である。また、各種製品開発においても、実際の製品における高級脂肪酸を始めとした有機酸の含有量をデータ化することは、試験水準を決定する上で重要な情報である。 The higher fatty acid may be used for purposes other than the surface treatment agent described above. On the other hand, in order to make inorganic powder exhibit desired characteristics, a mixture of a plurality of higher fatty acids and a variety of mixtures in which higher fatty acids are mixed with sugars, alcohols, and organic acids are also used. In order to obtain desired characteristics in the inorganic powder, organic substances such as higher fatty acids are managed in the production process as important management items in terms of both types and amounts. Therefore, quantifying the amount of organic substances such as higher fatty acids contained in various products including inorganic powder is an important matter in quality control. Also, in the development of various products, it is important information to determine the test level to make data on the content of organic acids such as higher fatty acids in actual products.
ここで高級脂肪酸を分析する方法としては、ガスクロマトグラフィー（本発明において「Ｇ．Ｃ」と記載する場合がある。）で分析可能な誘導体へ変化させた後、当該Ｇ．Ｃを用いて分析を行う方法がある（例えば、非特許文献１参照）。 Here, as a method of analyzing higher fatty acids, after changing to a derivative that can be analyzed by gas chromatography (in some cases, described as “GC” in the present invention), the G.C. There is a method of performing analysis using C (see, for example, Non-Patent Document 1).
無機粉体を始めとする各種製品への、高級脂肪酸を始めとした有機物の添加量等は、添加時における装置の制御により管理できる。しかし、実際にどの程度の量の高級脂肪酸を始めとした有機物が無機粉体に含有されているかを定量しようとする際には、上述したように複数の有機物が混在する為、正確な定量分析をするための試料調整に長時間を費やす為、製造工程へのフィードバックには間に合わない。即ち、工程管理に利用しながら無機粉体に含有されている高級脂肪酸を定量分析する方法がなかった。
本発明は、上述の状況の下で為されたものであり、その解決しようとする課題は、無機粉体、特に酸化銀粉に含有される高級脂肪酸量を、簡便且つ正確に定量分析出来る方法を提供することである。
The amount of organic substances such as higher fatty acids added to various products including inorganic powder can be managed by controlling the apparatus at the time of addition. However, when quantifying how much organic fatty acids, including higher fatty acids, are actually contained in inorganic powders, multiple organic substances are mixed as described above, so accurate quantitative analysis Because it takes a long time to prepare the sample to perform, it is not in time for feedback to the manufacturing process. That is, there has been no method for quantitative analysis of higher fatty acids contained in inorganic powders while utilizing for process control.
The present invention has been made under the above-described circumstances, and the problem to be solved is a method that can easily and accurately quantitatively analyze the amount of higher fatty acids contained in inorganic powder, particularly silver oxide powder. Is to provide.
上述の課題を解決する為、本発明者らは鋭意研究を行った。
そして、所定の溶媒を用いて溶媒抽出を行うことで、無機粉体に含まれる高級脂肪酸と、糖類、アルコールとを、９５％以上の精度をもって分離を出来るとの知見を得た。
次に、分離された高級脂肪酸を炭素分析計にて分析することで、高級脂肪酸量を迅速、簡便、且つ正確に定量分析可能であるとの知見を得て本発明を完成した。
In order to solve the above-mentioned problems, the present inventors have conducted intensive research.
And the knowledge that the higher fatty acid contained in inorganic powder, saccharide | sugar, and alcohol could be isolate | separated with an accuracy of 95% or more by performing solvent extraction using a predetermined | prescribed solvent was acquired.
Next, by analyzing the separated higher fatty acid with a carbon analyzer, the present invention was completed by obtaining the knowledge that the amount of higher fatty acid can be quantitatively analyzed quickly, simply and accurately.
すなわち、上述の課題を解決するための第１の発明は、
高級脂肪酸を含む無機粉体に酸を添加して、当該無機粉体を溶解し金属溶液とする工程と、
当該金属溶液へ、高級脂肪酸を溶解可能であり、２５℃で液体であり、沸点５０℃以下であり、水に不溶である有機溶媒を添加して混合した後、水相と有機相とに分離する工程と、
当該有機相から分取した有機相分取液の当該有機溶媒を除去し、残渣中の炭素量を測定する工程とを、有することを特徴とする無機粉体に含有される高級脂肪酸の定量分析方法である。
That is, the first invention for solving the above-described problem is:
Adding an acid to an inorganic powder containing a higher fatty acid to dissolve the inorganic powder into a metal solution;
A higher fatty acid can be dissolved in the metal solution, is liquid at 25 ° C., has a boiling point of 50 ° C. or less, and is mixed with an organic solvent that is insoluble in water, and then separated into an aqueous phase and an organic phase. And a process of
Removing the organic solvent from the organic phase fraction separated from the organic phase and measuring the amount of carbon in the residue, and quantitative analysis of higher fatty acids contained in the inorganic powder, Is the method.
第２の発明は、
前記有機溶媒として、四塩化炭素、ジクロロメタン、クロロホルムから選択される１種以上を用いることを第１の発明に記載の無機粉体に含有される高級脂肪酸の定量分析方法である。
The second invention is
In the method for quantitative analysis of higher fatty acids contained in the inorganic powder according to the first invention, one or more selected from carbon tetrachloride, dichloromethane, and chloroform is used as the organic solvent.
第３の発明は、
前記残渣中の炭素量を測定する方法として、炭素自動分析機を用いることを特徴とする第１または第２の発明に記載の無機粉体に含有される高級脂肪酸の定量分析方法である。
The third invention is
The method for quantitatively analyzing higher fatty acids contained in the inorganic powder according to the first or second invention, wherein an automatic carbon analyzer is used as a method for measuring the amount of carbon in the residue.
第４の発明は、
前記無機粉体が銀粉であることを特徴とする第１から第３の発明のいずれかに記載の無機粉体に含有される高級脂肪酸の定量分析方法である。
The fourth invention is:
The method for quantitative analysis of higher fatty acids contained in an inorganic powder according to any one of the first to third inventions, wherein the inorganic powder is silver powder.
本発明に係る無機粉体に含有される高級脂肪酸の定量分析方法によれば、導電性ペースト、銀電池等に使用される無機粉体に含有される高級脂肪酸を、簡便且つ正確に定量分析出来た。 According to the method for quantitative analysis of higher fatty acids contained in inorganic powders according to the present invention, higher fatty acids contained in inorganic powders used in conductive pastes, silver batteries and the like can be quantitatively analyzed simply and accurately. It was.
本発明は、無機粉体に含有される高級脂肪酸を、簡便且つ正確に定量分析出来る方法を提供することを目的とした発明である。無機粉体としては、酸化銀粉、酸化銅粉など、金属系の無機粉体に適応するのが好ましい。酸に溶解しやすいからである。
具体的には、無機粉体に表面処理剤として含有される高級脂肪酸とその他不純物との分離精製を行い、高級脂肪酸を単離すること。単離された高級脂肪酸のみを、９５％以上の高い回収率で回収すること。そして回収された高級脂肪酸を分析精度５％以内で分析することである。併せて、誘導体化等の高度な前処理を必要としない測定方法を探索し、測定時間（従来のＧＣ−ＭＳ、ＬＣの場合、１８時間程度掛かっていた。）を、３０分間程度に短縮することである。
そして、上述した無機粉体に含有される高級脂肪酸の簡便且つ正確な定量分析方法により、品質管理指標を得ることである。
An object of the present invention is to provide a method that enables simple and accurate quantitative analysis of higher fatty acids contained in inorganic powders. As the inorganic powder, it is preferable to adapt to a metal-based inorganic powder such as silver oxide powder and copper oxide powder. This is because it is easily dissolved in an acid.
Specifically, the higher fatty acid contained in the inorganic powder as a surface treatment agent and other impurities are separated and purified to isolate the higher fatty acid. Only isolated higher fatty acids should be recovered at a high recovery rate of 95% or higher. Then, the recovered higher fatty acid is analyzed with an analysis accuracy within 5%. In addition, a measurement method that does not require advanced pretreatment such as derivatization is searched, and the measurement time (in the case of conventional GC-MS and LC, takes about 18 hours) is shortened to about 30 minutes. That is.
Then, a quality control index is obtained by a simple and accurate quantitative analysis method for higher fatty acids contained in the inorganic powder described above.
本発明に係る無機粉体に含有される高級脂肪酸の定量分析方法について、図面を参照しながら説明する。
図１は、本発明に係る無機粉体に含有される高級脂肪酸の定量分析方法の操作を示すフロー図である。
被測定物は、銀電池等に使用される酸化銀粉等の無機粉体であって、高級脂肪酸（ステアリン酸等）、各種糖類、アルコール類等からなる表面処理剤を含有するものである。
当該被測定物を所定量（例えば、２ｇ）準備し、精密に秤量する。
A method for quantitative analysis of higher fatty acids contained in the inorganic powder according to the present invention will be described with reference to the drawings.
FIG. 1 is a flowchart showing the operation of the method for quantitative analysis of higher fatty acids contained in the inorganic powder according to the present invention.
The object to be measured is an inorganic powder such as silver oxide powder used in a silver battery or the like, and contains a surface treatment agent composed of higher fatty acids (such as stearic acid), various sugars, alcohols and the like.
A predetermined amount (for example, 2 g) of the object to be measured is prepared and weighed precisely.
精秤した被測定物へ酸を添加する。添加する酸としては、濃度６Ｍ〜１２Ｍの硝酸、濃度１Ｍ〜１２Ｍの塩酸等が好ましく使用できる。但し、無機粉体を溶解する際に生成する脂肪酸を遊離させるため、酸のプロトン濃度は高い方が望ましい。なお、本方法は、被測定物中の高級脂肪酸は１質量％以下の微量における場合も適用できる。
酸の添加量は、精秤した被測定物の反応当量に比して過剰量を加える。例えば、濃度６Ｍ〜１０Ｍの硝酸を用いるなら２０ｍｌを加える。尚、当該酸の純度は、試薬特級水準であることが好ましい。
被測定物を酸に溶解させ被測定物溶液を得る。この溶解の際、混合物の温度が５０℃以下を保つように留意する。これは、金属イオンと高級脂肪酸とが石鹸を形成する反応を回避する為である。さらに、混合物へ超音波を照射し、被測定物の酸への溶解を促進することも好ましい構成である。
詳細は後述するが、被測定物溶液のｐＨ値は３以下とすること好ましい。当該構成を採ることで、次工程において高級脂肪酸を安定的に有機相へ移行させることが出来る。
Add acid to the weighed object. As the acid to be added, nitric acid having a concentration of 6M to 12M, hydrochloric acid having a concentration of 1M to 12M and the like can be preferably used. However, it is desirable that the acid proton concentration is high in order to liberate the fatty acid produced when the inorganic powder is dissolved. In addition, this method is applicable also when the higher fatty acid in a to-be-measured object is in the trace amount of 1 mass% or less.
The acid is added in an excess amount compared to the reaction equivalent of the precisely measured object. For example, if using nitric acid with a concentration of 6M to 10M, add 20 ml. In addition, it is preferable that the purity of the said acid is a reagent special grade level.
A measurement object solution is obtained by dissolving the measurement object in an acid. Care is taken to keep the temperature of the mixture below 50 ° C. during this dissolution. This is to avoid the reaction between metal ions and higher fatty acids forming soap. Furthermore, it is also preferable to irradiate the mixture with ultrasonic waves to promote dissolution of the object to be measured in the acid.
Although details will be described later, the pH value of the solution to be measured is preferably 3 or less. By adopting this configuration, higher fatty acids can be stably transferred to the organic phase in the next step.
ここで、上述した酸の添加による、高級脂肪酸の遊離について説明する。
まず、被測定物へ酸として硝酸を添加した場合、（式１）の反応が進行すると考えられる。
一方、（式１）と同時に（式２）も進行する。
Ａｇ：（高級脂肪酸、高級脂肪酸イオン、アルコール、糖）＋ＨＮＯ３→Ａｇ＋＋ＮＯ２＋高級脂肪酸（高級脂肪酸イオン）＋Ｈ２Ｏ・・・（式１）
（式１）の反応により、ＡｇはＡｇ＋となり、アルコール、糖は酸化されてＨ２ＯとＣＯ２となり、ＣＯ２は揮散するか炭酸となる。
高級脂肪酸イオン＋Ｈ＋→高級脂肪酸・・・（式２）
（式２）の反応により、高級脂肪酸イオンは酸化されて高級脂肪酸となる。
結局、（式１）（式２）の進行により、当初のＡｇ：（高級脂肪酸、高級脂肪酸イオン、アルコール、糖）は、Ａｇ＋＋ＮＯ２＋高級脂肪酸＋Ｈ２Ｏとなる。
Here, the liberation of higher fatty acids by addition of the above-described acid will be described.
First, when nitric acid is added as an acid to the object to be measured, the reaction of (Formula 1) is considered to proceed.
On the other hand, (Expression 2) proceeds simultaneously with (Expression 1).
Ag: (higher fatty acid, higher fatty acid ion, alcohol, sugar) + HNO 3 → Ag + + NO 2 + higher fatty acid (higher fatty acid ion) + H 2 O (Formula 1)
By the reaction of (Formula 1), Ag becomes Ag + , alcohol and sugar are oxidized to H 2 O and CO 2 , and CO 2 is volatilized or becomes carbonic acid.
Higher fatty acid ion + H + → higher fatty acid ... (Formula 2)
By the reaction of (Formula 2), the higher fatty acid ion is oxidized to a higher fatty acid.
Eventually, with the progression of (Formula 1) and (Formula 2), the initial Ag: (higher fatty acid, higher fatty acid ion, alcohol, sugar) becomes Ag + + NO 2 + higher fatty acid + H 2 O.
被測定物溶液の液温が常温（２５℃）となったら、ここへ有機溶媒を添加する。
当該有機溶媒は、高級脂肪酸を溶解可能であり、２５℃で液体であり、沸点５０℃以下であり、水に不溶であるものが求められる。本発明者らは、（式１）（式２）で説明した高級脂肪酸は十分に溶解する一方、２５℃で液体であり、沸点５０℃以下であり、水に不溶な有機溶媒の好ましい例としてジクロロメタンを知見した。ジクロロメタンは、遊離した高級脂肪酸を抽出するのに適していると考えられる。
When the liquid temperature of the solution to be measured reaches room temperature (25 ° C.), an organic solvent is added thereto.
The organic solvent is required to be able to dissolve higher fatty acids, be liquid at 25 ° C., have a boiling point of 50 ° C. or lower, and be insoluble in water. As a preferred example of the organic solvent in which the higher fatty acid described in (Formula 1) and (Formula 2) is sufficiently dissolved, it is liquid at 25 ° C., has a boiling point of 50 ° C. or less, and is insoluble in water. Dichloromethane was found. Dichloromethane is considered suitable for extracting free higher fatty acids.
有機溶媒の添加量は、被測定物溶液量と同量程度で良い。また、後述する溶媒蒸発時に揮発除去を迅速化するため、低沸点溶媒（４０℃程度）であることが好ましいが、ジクロロメタンの沸点は４０℃でありこの点でも好ましい。
被測定物溶液と有機溶媒との混合物を十分に撹拌する。撹拌方法としては、振とう撹拌等が好ましい。
The amount of the organic solvent added may be about the same as the amount of the solution to be measured. Moreover, in order to expedite volatilization removal at the time of solvent evaporation described later, a low boiling point solvent (about 40 ° C.) is preferable, but dichloromethane has a boiling point of 40 ° C., which is also preferable in this respect.
The mixture of the solution to be measured and the organic solvent is sufficiently stirred. As the stirring method, shaking stirring or the like is preferable.
被測定物溶液と有機溶剤との混合物を、水相と有機相とに分液する。分液の際、前記混合物を遠心分離することで分液を早く完了でき好ましい構成である。今回の混合物のように４０ｍｌ程度の量であれば、３０００ｒｐｍ、１０分間程度の遠心分離をすることで分液を完了出来る。
分液が完了したら水相と有機相とを分け、有機層から所定量の試料を分取する。分取量は、例えば２ｍｌで良い。
A mixture of the solution to be measured and the organic solvent is separated into an aqueous phase and an organic phase. In the case of liquid separation, the mixture can be completed quickly by centrifuging the mixture, which is a preferable configuration. Separation can be completed by centrifuging at 3000 rpm for about 10 minutes if the amount is about 40 ml as in the current mixture.
When the separation is completed, the aqueous phase and the organic phase are separated, and a predetermined amount of sample is collected from the organic layer. For example, the fraction can be 2 ml.
当該分取試料を多孔質ボードに含浸させた後、当該ボードをドラフト内にて５０℃ ０．５時間加熱して有機溶媒を蒸発乾燥させて乾固させ残渣を得た。当該有機溶媒が蒸散した多孔質のボードを炭素分析計に装填し、測定された炭素量から、銀粉に含有された高級脂肪酸の炭素量が測定された。ここで、予め銀粉に含有された表面処理剤中における高級脂肪酸の種類と含有量とを確認しておけば、当該測定された炭素量から、銀粉に含有された高級脂肪酸の種類と含有量とを算定出来る。 After the preparative sample was impregnated into a porous board, the board was heated in a draft at 50 ° C. for 0.5 hour to evaporate and dry the organic solvent to obtain a residue. A porous board vaporized with the organic solvent was loaded into a carbon analyzer, and the carbon content of the higher fatty acid contained in the silver powder was measured from the measured carbon content. Here, if the type and content of the higher fatty acid in the surface treatment agent previously contained in the silver powder are confirmed, from the measured carbon amount, the type and content of the higher fatty acid contained in the silver powder Can be calculated.
（炭素分析計の校正と検量線の作成）
本発明に係る無機粉体に含有される高級脂肪酸の定量分析方法に用いる炭素分析計の校正と検量線の作成について説明する。
炭素分析計の校正と検量線の作成の具体的方法について説明する。
（１）炭素分析計を鉄鋼標準物質で校正する。
（２）既知量のステアリン酸を含むジクロロメタン溶液を所定量採取し、炭素自動分析機用素焼きボードに浸透させる。
（３）炭素自動分析機用素焼きボードに浸透させた既知量のステアリン酸を含むジクロロメタン溶液を蒸発乾固し、炭素分析計で測定し、ステアリン酸量を算定した。
（４）ステアリン酸の既知量と、炭素分析計で測定し算定したステアリン酸量とを比較して検量線を作成し、分析精度も確認した。当該検量線を図２に示す。
(Calibration of carbon analyzer and creation of calibration curve)
The calibration of a carbon analyzer used for the quantitative analysis method for higher fatty acids contained in the inorganic powder according to the present invention and the creation of a calibration curve will be described.
A specific method for calibrating the carbon analyzer and creating a calibration curve will be described.
(1) Calibrate the carbon analyzer with steel standards.
(2) A predetermined amount of a dichloromethane solution containing a known amount of stearic acid is collected and permeated into an unglazed board for an automatic carbon analyzer.
(3) A dichloromethane solution containing a known amount of stearic acid permeated into an unglazed board for a carbon automatic analyzer was evaporated to dryness, measured with a carbon analyzer, and the amount of stearic acid was calculated.
(4) A calibration curve was created by comparing the known amount of stearic acid with the amount of stearic acid measured and calculated with a carbon analyzer, and the analytical accuracy was also confirmed. The calibration curve is shown in FIG.
図２は縦軸にステアリン酸の測定値をとり、横軸にステアリン酸の既知量をとったグラフである。
図３より分析精度は、変動係数として１．４％（ｎ＝３）であることが判明した。
FIG. 2 is a graph with the measured value of stearic acid on the vertical axis and the known amount of stearic acid on the horizontal axis.
From FIG. 3, the analysis accuracy was found to be 1.4% (n = 3) as a coefficient of variation.
（有機相への高級脂肪酸抽出率のｐＨ依存性）
上述した（式２）に関連して、高級脂肪酸（ステアリン酸等）の有機相への抽出率が、被測定物溶液のｐＨ値にどの様に依存性するかについて検討した結果について説明する。
まず検討用試料を調製した。
純水２０ｍｌにステアリン酸２０ｇを加えた後、硝酸または水酸化ナトリウムを添加して、ｐＨ値が０、３、５、７および９の５種の試料を調製した。当該試料へそれぞれジクロロメタン２０ｍｌを添加して検討用試料を調製した。
当該検討用試料を５分間振とう撹拌し分液を完了してから、有機相中に抽出されたステアリン酸量の定量値を、上述した方法により測定した。
当該測定結果を図３に示す。図３は縦軸にステアリン酸の抽出率、横軸に試料のｐＨ値をとったグラフである。
図３より、試料のｐＨ値が３以下であればステアリン酸の抽出率が９５質量％を超え安定していることが判明した。
(PH dependence of higher fatty acid extraction rate into organic phase)
In relation to (Equation 2) described above, the results of studying how the extraction rate of higher fatty acids (such as stearic acid) into the organic phase depends on the pH value of the solution to be measured will be described.
First, a sample for study was prepared.
After adding 20 g of stearic acid to 20 ml of pure water, nitric acid or sodium hydroxide was added to prepare 5 types of samples having pH values of 0, 3, 5, 7, and 9. A sample for examination was prepared by adding 20 ml of dichloromethane to each of the samples.
After the sample for examination was shaken and stirred for 5 minutes to complete the separation, the quantitative value of the amount of stearic acid extracted into the organic phase was measured by the method described above.
The measurement results are shown in FIG. FIG. 3 is a graph in which the vertical axis represents the stearic acid extraction rate and the horizontal axis represents the pH value of the sample.
From FIG. 3, it was found that when the pH value of the sample was 3 or less, the extraction rate of stearic acid exceeded 95% by mass and was stable.
（まとめ）
本発明では、表面処理剤（高級脂肪酸）を含む無機粉体へ、反応当量に対して大過剰の酸を添加し、低温で溶解した。そして、得られた金属溶解液を、高級脂肪酸を溶解可能であり、２５℃で液体であり、沸点５０℃以下であり、且つ水に不溶である有機溶媒で抽出することにより、表面処理剤中の高級脂肪酸を９５％以上の回収率で抽出した。
次に、当該有機相から所定量の試料を分種し、当該試料を５０℃で蒸発乾燥して乾固した後、残渣を炭素分析計で測定した。測定された炭素量から高級脂肪酸濃度を計算したものである。
(Summary)
In the present invention, a large excess of acid with respect to the reaction equivalent is added to the inorganic powder containing the surface treating agent (higher fatty acid) and dissolved at a low temperature. Then, the obtained metal solution is extracted with an organic solvent that can dissolve higher fatty acids, is liquid at 25 ° C., has a boiling point of 50 ° C. or less, and is insoluble in water. The higher fatty acids were extracted with a recovery rate of 95% or more.
Next, a predetermined amount of the sample was separated from the organic phase, the sample was evaporated to dryness at 50 ° C., and the residue was measured with a carbon analyzer. The higher fatty acid concentration is calculated from the measured carbon content.
具体的には、無機粉体を低温溶解させることで、分解後の金属イオンと脂肪酸の結合（金属石けんの生成）を防止し、溶媒抽出を容易にした。
所定の有機溶媒を有機相に用いた溶媒抽出法により、表面処理剤中不純物である糖類，アルコールと、目的物質である高級脂肪酸との分離を９５％以上で可能にした。
高級脂肪酸を含む有機相の所定量を蒸発乾固し、残渣の炭素分析を行うことで、迅速かつ再現精度の高いデータが得られた（ｎ＝３、変動係数＝１．４ ％）。
本発明に係る高級脂肪酸の定量分析方法は誘導体化処理を必要としないため，操作手順が簡略化された（誘導体化処理では１８時間程度かかっていたが、本発明では試料の蒸発乾燥後３０分間程度で終了出来た。）。
Specifically, by dissolving the inorganic powder at a low temperature, the bond between metal ions and fatty acids after decomposition (generation of metal soap) was prevented, and solvent extraction was facilitated.
The solvent extraction method using a predetermined organic solvent in the organic phase enabled separation of sugars and alcohols as impurities in the surface treatment agent and higher fatty acids as target substances at 95% or more.
A predetermined amount of the organic phase containing higher fatty acids was evaporated to dryness, and carbon analysis of the residue was performed to obtain data with high speed and high reproducibility (n = 3, coefficient of variation = 1.4%).
Since the method for quantitative analysis of higher fatty acids according to the present invention does not require derivatization treatment, the operation procedure is simplified (the derivatization treatment took about 18 hours, but in the present invention, 30 minutes after evaporating and drying the sample. I was able to finish it with a degree.)
この結果、無機粉体に含有される高級脂肪酸の定量分析方法においては、分析にＧＣ−ＭＳやＬＣ−ＭＳの使用が不要な為、誘導体化等のステップが不要になり、定量操作が簡便、容易になった。さらに、従来の技術に係る誘導体化・ＧＣ−ＭＳで測定では、定量化が困難な為、品質管理項目として求められる高級脂肪酸量の定量性を確保出来ていなかったが、本発明により可能となった。 As a result, in the method for quantitative analysis of higher fatty acids contained in the inorganic powder, since the use of GC-MS or LC-MS is unnecessary for the analysis, steps such as derivatization are unnecessary, and the quantitative operation is simple. It became easy. Furthermore, since quantification is difficult in the derivatization / GC-MS measurement according to the prior art, the quantitativeness of the higher fatty acid amount required as a quality control item has not been ensured, but the present invention makes it possible. It was.
実施例を参照しながら、本発明をより具体的に説明する。
攪拌下においてＡｇ濃度５０ｇ／ｌ の硝酸銀水溶液に、当量（炭酸ナトリウム／Ａｇのモル比０．５）の炭酸ナトリウム水溶液を加え、ｐＨが５．５〜６．５となるように硝酸とアンモニア水とでｐＨを調整しながら、炭酸銀の沈殿の析出、成長、顆粒化までの工程における溶解、析出を繰り返すことにより沈殿を得た。この沈殿を洗浄、濾過し、１００℃で乾燥させた後徐々に昇温させ最大温度２５０℃で乾燥、加熱分解して酸化銀粉末を得た。
The present invention will be described more specifically with reference to examples.
Under stirring, an equivalent amount of sodium carbonate aqueous solution (sodium carbonate / Ag molar ratio 0.5) is added to an aqueous silver nitrate solution having an Ag concentration of 50 g / l, and nitric acid and aqueous ammonia so that the pH becomes 5.5 to 6.5. The precipitate was obtained by repeating dissolution and precipitation in the steps up to precipitation, growth and granulation of the silver carbonate while adjusting the pH. This precipitate was washed, filtered, dried at 100 ° C., gradually heated, dried at a maximum temperature of 250 ° C., and thermally decomposed to obtain a silver oxide powder.
１Ｌビーカーに純水４６３ｇをとり、上記得られた酸化銀粉２０ｇと、当該酸化銀粉に対して高級脂肪酸量が０．３６質量％となるように表面処理剤としてセラミック材料の添加剤である中京油脂株式会社製 セロゾール（高級脂肪酸、多種有機物含）を０．４６５ｇ添加し、２．３３質量％の酸化銀スラリーを得た。そして当該酸化銀スラリーより、ブフナー漏斗を用いて固形分を採取した。続いて、ブフナー漏斗を用いて当該固形分を水洗し、７０℃大気中において１２時間乾燥した。当該乾燥物を４２５メッシュの篩を通し、篩下として実施例に係る表面処理剤を含む酸化銀粉試料を得た。得られた試料粉の物性を測定した結果。比表面積は、ＢＥＴ１点法により、０．３１ｍ２／ｇ、Ｄ５０平均粒径は、マイクロトラックによる測定の結果、１４．４μｍであった。 Take 463 g of pure water in a 1 L beaker, 20 g of the obtained silver oxide powder, and Chukyo Yushi, which is an additive for ceramic materials as a surface treatment so that the amount of higher fatty acid is 0.36% by mass with respect to the silver oxide powder 0.465 g of Cerosol (including higher fatty acids and various organic substances) was added to obtain 2.33% by mass of silver oxide slurry. And solid content was extract | collected from the said silver oxide slurry using the Buchner funnel. Subsequently, the solid content was washed with water using a Buchner funnel and dried in the atmosphere at 70 ° C. for 12 hours. The dried product was passed through a 425 mesh sieve, and a silver oxide powder sample containing the surface treatment agent according to the example was obtained as a sieve. The result of measuring the physical properties of the obtained sample powder. The specific surface area was 0.31 m 2 / g according to the BET 1- point method, and the D50 average particle size was 14.4 μm as a result of measurement using a microtrack.
得られた実施例に係る表面処理剤を含む酸化銀粉２ｇを精密に秤量し、濃度６Ｍの硝酸（試薬特級）２０ｍｌを加え、混合物の温度を５０℃以下に保ちながら超音波を照射し、酸化銀粉を溶解した。溶液の液温が２５℃となったらジクロロメタン２０ｍｌを加え、振とう撹拌により十分に撹拌した後、３０００ｒｐｍ、１０分間遠心分離し、静置して水相と有機相とに分液した。そして、有機層から２ｍｌの試料を分取し、炭素自動分析機用素焼きボードに含浸させた。そして当該素焼きボードをドラフト中、５０℃で、０．５時間設置し、ジクロロメタンを蒸発させて、残留物を蒸発乾固させた。そして当該素焼きボードを炭素自動分析機に装填し、得られた残留物中の炭素量を測定した。 2 g of silver oxide powder containing the surface treating agent according to the obtained examples was precisely weighed, 20 ml of nitric acid (reagent special grade) with a concentration of 6M was added, and ultrasonic waves were irradiated while maintaining the temperature of the mixture at 50 ° C. or lower to oxidize. Silver powder was dissolved. When the liquid temperature of the solution reached 25 ° C., 20 ml of dichloromethane was added, and after sufficient stirring by shaking and stirring, the solution was centrifuged at 3000 rpm for 10 minutes and allowed to stand to separate into an aqueous phase and an organic phase. Then, a 2 ml sample was taken from the organic layer and impregnated on an unglazed board for an automatic carbon analyzer. The unglazed board was placed in a draft at 50 ° C. for 0.5 hour to evaporate dichloromethane and evaporate the residue to dryness. Then, the unglazed board was loaded into an automatic carbon analyzer, and the amount of carbon in the obtained residue was measured.
測定された炭素は、全て酸化銀粉に付着した高級脂肪酸に由来し、高級脂肪酸中のステアリン酸およびパルミチン酸の配合量は維持されていると仮定して、ステアリン酸量を算定したところ、酸化銀粉に対して０．３３質量％であることが判明した。当該０．３３質量％という値は、当初の仕込み量が０．３６質量％であることから考えて、高精度な結果であると考えられる。
当該ステアリン酸量の結果を得るまでの時間は、表面処理剤を含む酸化銀粉２ｇを精密に秤量した時点から、１検体当り２０分間（１検体当り１０試料を分析）であった。
The measured carbon was derived from the higher fatty acid adhering to the silver oxide powder, and the amount of stearic acid was calculated on the assumption that the amount of stearic acid and palmitic acid contained in the higher fatty acid was maintained. It was found that the content was 0.33 mass%. The value of 0.33% by mass is considered to be a highly accurate result considering that the initial charging amount is 0.36% by mass.
The time until the result of the amount of stearic acid was obtained was 20 minutes per sample (analyze 10 samples per sample) from the time when 2 g of silver oxide powder containing the surface treatment agent was precisely weighed.
尚、上述の仮定を確認するため、表面処理剤を含む酸化銀粉表面のＦＴ−ＩＲスペクトルを測定し図４に示した。次に、有機層から分取した試料の残留物のＦＴ−ＩＲスペクトルを測定し図５に示した。さらに、試薬特級グレードのステアリン酸をのＦＴ−ＩＲスペクトルを測定し図６に示した。
図４と図６の比較より、酸化銀粉表面の表面処理剤は高級脂肪酸と、糖類およびアルコール類を含有していることが含むことが判明した。一方、図５と図６の比較より、ジクロロメタン中には高級脂肪酸のみが抽出されていることが判明した。
In addition, in order to confirm the above-mentioned assumption, the FT-IR spectrum of the silver oxide powder surface containing a surface treating agent was measured and shown in FIG. Next, the FT-IR spectrum of the residue of the sample fractionated from the organic layer was measured and shown in FIG. Furthermore, the FT-IR spectrum of the reagent grade stearic acid was measured and shown in FIG.
From the comparison between FIG. 4 and FIG. 6, it was found that the surface treatment agent on the surface of the silver oxide powder contained higher fatty acids, sugars and alcohols. On the other hand, it was found from the comparison between FIG. 5 and FIG. 6 that only higher fatty acids were extracted in dichloromethane.
図７は、有機層から分取した試料の残留物をエステル化し、ｎ−へキサン抽出したものをカラム精製し、Ｇ．Ｃ−ＭＳで測定した結果を示すチャートである。
当該チャートから、試料の残留物はステアリン酸エステルとパルミチンサンエステルであることが確認出来た。
FIG. 7 shows a column purification of a sample obtained by esterifying a residue collected from an organic layer and extracting n-hexane. It is a chart which shows the result measured by C-MS.
From the chart, it was confirmed that the residue of the sample was stearic acid ester and palmitic sun ester.
Claims (4)
当該金属溶液へ、高級脂肪酸を溶解可能であり、２５℃で液体であり、沸点５０℃以下であり、水に不溶である有機溶媒を添加して混合した後、水相と有機相とに分離する工程と、
当該有機相から分取した有機相分取液の当該有機溶媒を除去し、残渣中の炭素量を測定する工程とを、有することを特徴とする無機粉体に含有される高級脂肪酸の定量分析方法。 Adding an acid to an inorganic powder containing a higher fatty acid to dissolve the inorganic powder into a metal solution;
A higher fatty acid can be dissolved in the metal solution, is liquid at 25 ° C., has a boiling point of 50 ° C. or less, and is mixed with an organic solvent that is insoluble in water, and then separated into an aqueous phase and an organic phase. And a process of
Removing the organic solvent from the organic phase fraction separated from the organic phase and measuring the amount of carbon in the residue, and quantitative analysis of higher fatty acids contained in the inorganic powder, Method.
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| KR20210016031A (en) | 2018-07-30 | 2021-02-10 | 니뽄 다바코 산교 가부시키가이샤 | Perfume-containing sheet manufacturing apparatus and flavor-containing sheet manufacturing method |
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| KR20190077434A (en) | 2016-11-30 | 2019-07-03 | 니뽄 다바코 산교 가부시키가이샤 | A fragrance-containing sheet for smoking articles and a smoking article containing the same |
| KR20210016031A (en) | 2018-07-30 | 2021-02-10 | 니뽄 다바코 산교 가부시키가이샤 | Perfume-containing sheet manufacturing apparatus and flavor-containing sheet manufacturing method |
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