JP2017181284A - Method of quantifying component of rubber composition - Google Patents
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Abstract
Description
本発明はゴム組成物中の成分の定量方法に関する。 The present invention relates to a method for quantifying components in a rubber composition.
例えば、タイヤのようなゴム製品は、ゴム組成物を用いて形成される。このゴム組成物は、ゴム成分以外に様々な成分を含んでいる。この成分として、しゃっかい剤、老化防止剤、加硫促進剤、加工助剤、光安定剤、可塑剤、軟化剤、加硫促進助剤、カップリング剤などが挙げられる。ゴム製品の性能把握の観点、問題解決の観点などから、ゴム組成物に含まれる成分を定性し、この成分の量を定量することが極めて重要である。 For example, a rubber product such as a tire is formed using a rubber composition. This rubber composition contains various components in addition to the rubber component. Examples of this component include a masking agent, an antioxidant, a vulcanization accelerator, a processing aid, a light stabilizer, a plasticizer, a softening agent, a vulcanization acceleration aid, and a coupling agent. From the viewpoint of grasping the performance of rubber products and from the viewpoint of solving problems, it is extremely important to qualify the components contained in the rubber composition and quantify the amount of these components.
ゴム組成物に含まれる成分の定性または定量には、ガスクロマトグラフ、液体クロマトグラフ等の機器を用いるのが一般的である（特許文献１〜３など参照）。 For qualitative or quantitative determination of the components contained in the rubber composition, it is common to use an instrument such as a gas chromatograph or a liquid chromatograph (see Patent Documents 1-3).
通常のゴム組成物中の成分の分析方法として、ゴム製品から切り出したゴム組成物の溶媒抽出液を前記の機器を用いた分析に用いる方法がある。一方、抽出物ではなく、ゴム製品から切り出したゴム組成物試料を直接機器に導入して分析する方法として、熱分解ガスクロマトグラフィーがある。この熱分解ガスクロマトグラフィーでは、ゴム組成物試料は熱分解されて気相成分を生成する。この気相成分がキャリアーガスに載せられて分離カラムに導入されて分離される。 As a method for analyzing components in a normal rubber composition, there is a method in which a solvent extract of a rubber composition cut out from a rubber product is used for analysis using the above-mentioned instrument. On the other hand, pyrolysis gas chromatography is a method for analyzing a rubber composition sample cut from a rubber product instead of an extract directly into an instrument. In this pyrolysis gas chromatography, a rubber composition sample is pyrolyzed to produce a gas phase component. This gas phase component is placed on a carrier gas, introduced into a separation column, and separated.
溶媒抽出液を分析に用いる場合、分子量が大きい成分の抽出が困難であるという問題や、定量性に劣るという問題がある。また、ゴム組成物試料を直接、熱分解ガスクロマトグラフィーにより分析する方法では、感度が低く、微量しか含有していない成分を定量することは困難である。 When a solvent extract is used for analysis, there are problems that it is difficult to extract components having a large molecular weight, and that quantitative properties are poor. Further, in a method of directly analyzing a rubber composition sample by pyrolysis gas chromatography, it is difficult to quantify a component having low sensitivity and containing only a trace amount.
本発明は、微量しか含有していない成分をも定量できるゴム組成物中の成分の定量方法を提供することを目的とする。 An object of this invention is to provide the determination method of the component in the rubber composition which can also quantify the component which contains only a trace amount.
本発明は、ゴム組成物中の成分の定量方法であり、標準試料を含むゴム組成物の溶媒抽出物を熱分解ガスクロマトグラフ質量分析計により分析して得られたクロマトグラムにおける標準試料に由来するピークのピーク面積と定量対象成分に由来するピークのピーク面積との比に基づいて定量する定量方法に関する。 The present invention is a method for quantifying components in a rubber composition, and is derived from a standard sample in a chromatogram obtained by analyzing a solvent extract of a rubber composition containing a standard sample with a pyrolysis gas chromatograph mass spectrometer. The present invention relates to a quantification method for quantification based on a ratio between a peak area of a peak and a peak area of a peak derived from a quantification target component.
前記定量対象成分がしゃっかい剤であることが好ましい。 It is preferable that the component to be quantified is a crushing agent.
本発明のゴム組成物中の成分の定量方法によれば、微量しか含有していない成分をも定量することができる。 According to the method for quantifying components in the rubber composition of the present invention, a component containing only a trace amount can be quantified.
本発明のゴム組成物中の成分の定量方法は、標準試料を含むゴム組成物の溶媒抽出物を熱分解ガスクロマトグラフ質量分析計（ＧＣＭＳ）により分析することを特徴とし、得られたクロマトグラムにおける標準試料に由来するピークのピーク面積と定量対象成分に由来するピークのピーク面積との比に基づいて定量する定量方法である。 The method for quantifying components in the rubber composition of the present invention comprises analyzing a solvent extract of a rubber composition containing a standard sample with a pyrolysis gas chromatograph mass spectrometer (GCMS). This is a quantification method in which quantification is performed based on the ratio between the peak area of a peak derived from a standard sample and the peak area of a peak derived from a component to be quantified.
本発明の定量方法は、標準試料を含むゴム組成物の溶媒抽出液を得る抽出工程、溶媒抽出液を乾固させて溶媒抽出物を得る乾固工程、溶媒抽出物をＧＣＭＳにより分析する分析工程、分析工程で得られた定量対象成分および標準試料の結果から、対象成分を定量する定量工程を含む定量方法とすることが好ましい。 The quantification method of the present invention includes an extraction step for obtaining a solvent extract of a rubber composition containing a standard sample, a drying step for obtaining a solvent extract by drying the solvent extract, and an analysis step for analyzing the solvent extract by GCMS. It is preferable to use a quantification method including a quantification step for quantifying the target component from the results of the quantification target component and the standard sample obtained in the analysis step.
前記抽出工程は、標準試料を含むゴム組成物の溶媒抽出液を得る工程である。標準試料はゴム組成物試料を抽出溶媒で抽出して得られた抽出液に特定の濃度となるように添加してもよいし、あらかじめ特定濃度となるように標準試料が添加された抽出溶媒を用いてゴム組成物試料を抽出してもよい。 The extraction step is a step of obtaining a solvent extract of a rubber composition containing a standard sample. The standard sample may be added to the extract obtained by extracting the rubber composition sample with the extraction solvent so as to have a specific concentration, or the extraction solvent to which the standard sample has been added in advance so that the specific concentration is obtained. It may be used to extract a rubber composition sample.
標準試料としては、揮発しない成分であり、ＧＣＭＳにより検出可能な成分であれば特に限定されず、ジベンゾチオフェン、アントラセン、フェナントレン、ドデカン、安息香酸ベンジルなどが挙げられる。なかでも、定量対象成分とＧＣＭＳにより検出されるピークが、重複しないものが好ましい。 The standard sample is not particularly limited as long as it is a component that does not volatilize and can be detected by GCMS, and examples include dibenzothiophene, anthracene, phenanthrene, dodecane, and benzyl benzoate. Among them, it is preferable that the component to be quantified and the peak detected by GCMS do not overlap.
抽出工程に用いるゴム組成物試料の調整は特に限定されないが、抽出効率に優れることから０．５〜１．５ｍｍの立方体状に裁断したものの質量を精秤することが好ましい。この質量は、定量精度の観点から１５０μｇ以上が好ましく、１９０μｇ以上がより好ましい。また、この質量は、２５０μｇ以下が好ましく、２１０μｇ以下がより好ましい。溶媒抽出物の精秤に用いるはかりの最小表示は０．１μｇ以下が好ましい。このようなはかりとしては、メトラートレド社製の商品名「ＸＰ２Ｕ ウルトラミクロ天びん」などが挙げられる。 Although adjustment of the rubber composition sample used for an extraction process is not specifically limited, Since it is excellent in extraction efficiency, it is preferable to precisely measure the mass of what was cut | judged to the 0.5-1.5 mm cube shape. This mass is preferably 150 μg or more, and more preferably 190 μg or more from the viewpoint of quantitative accuracy. The mass is preferably 250 μg or less, and more preferably 210 μg or less. The minimum display of the scale used for the precise balance of the solvent extract is preferably 0.1 μg or less. Examples of such scales include trade name “XP2U Ultra Micro Balance” manufactured by METTLER TOLEDO.
抽出溶媒としては、アセトン、テトラヒドロフラン、クロロホルム、トルエン、キシレン、２−プロパノール、メタノール、エタノール、酢酸エチル、ヘキサン、アセトニトリルなどが挙げられる。なかでも、溶出力に優れることから、アセトン、テトラヒドロフラン、クロロホルムが好ましく、アセトンがより好ましい。 Examples of the extraction solvent include acetone, tetrahydrofuran, chloroform, toluene, xylene, 2-propanol, methanol, ethanol, ethyl acetate, hexane, and acetonitrile. Of these, acetone, tetrahydrofuran, and chloroform are preferable, and acetone is more preferable because of its excellent dissolution power.
ゴム組成物試料（ｍｇ）に対する抽出溶媒量（ｍｌ）は特に限定されないが、十分な抽出効率が得られるという観点から、１（ｍｇ／ｍｌ）以上が好ましく、２０（ｍｇ／ｍｌ）以上がより好ましい。また、抽出溶媒の量の上限は特に限定されないが、作業性の観点から、２００（ｍｇ／ｍｌ）以下が好ましく、１５０（ｍｇ／ｍｌ）以下がより好ましい。 The amount of extraction solvent (ml) relative to the rubber composition sample (mg) is not particularly limited, but is preferably 1 (mg / ml) or more, more preferably 20 (mg / ml) or more from the viewpoint of obtaining sufficient extraction efficiency. preferable. The upper limit of the amount of the extraction solvent is not particularly limited, but is preferably 200 (mg / ml) or less, more preferably 150 (mg / ml) or less from the viewpoint of workability.
ゴム組成物試料を抽出溶媒に浸漬する方法は特に限定されず、従来の浸漬法などが挙げられる。浸漬法とする場合は２０〜５０℃の条件下で、１２〜１００時間、暗所で静置する方法が好ましい。浸漬の後、ガラス繊維フィルターや樹脂フィルターにより濾過することで溶媒抽出液を得ることができる。 The method for immersing the rubber composition sample in the extraction solvent is not particularly limited, and includes a conventional immersing method. When it is set as the immersion method, the method of leaving still in a dark place on the conditions of 20-50 degreeC for 12 to 100 hours is preferable. After immersion, a solvent extract can be obtained by filtering with a glass fiber filter or a resin filter.
前記乾固工程は、抽出工程で得られた溶媒抽出液から乾燥などにより溶媒を除去することで、固体成分の濃縮物または固体成分のみの溶媒抽出物を得る工程である。抽出溶媒の乾燥方法としては特に限定されず、従来の方法を採用することができる。なかでも、乾燥時間を短縮できるという理由から、減圧乾燥が好ましい。 The drying step is a step of obtaining a solid component concentrate or a solid component-only solvent extract by removing the solvent from the solvent extract obtained in the extraction step by drying or the like. The method for drying the extraction solvent is not particularly limited, and a conventional method can be adopted. Among these, vacuum drying is preferable because the drying time can be shortened.
前記分析工程は、溶媒抽出物をＧＣＭＳにより、標準試料に由来するピークと定量対象成分に由来するピークとを検出する工程である。ＧＣＭＳは、試料を熱分解装置により加熱し、この加熱により生成する気相成分に含まれる個々の成分を分離カラムにより分離し、単離された各成分を質量分析計により分析する方法である。 The analysis step is a step of detecting a peak derived from the standard sample and a peak derived from the component to be quantified by GCMS of the solvent extract. GCMS is a method in which a sample is heated by a thermal decomposition apparatus, individual components contained in gas phase components generated by this heating are separated by a separation column, and each isolated component is analyzed by a mass spectrometer.
前記熱分解装置としては、フロンティア・ラボ（株）製の縦型マイクロ電気炉型パイロライザー（商品名：ＰＹ−２０２０ｉＤ）などが挙げられる。なお、試料が架橋ゴムからなる場合、熱分解の容易性の観点から、熱分解の温度は５００℃以上６００℃以下が好ましい。 Examples of the thermal decomposition apparatus include a vertical micro electric furnace type pyrolyzer (trade name: PY-2020iD) manufactured by Frontier Laboratories. In addition, when a sample consists of crosslinked rubber, the temperature of thermal decomposition has preferable 500 to 600 degreeC from a viewpoint of the ease of thermal decomposition.
前記分離カラムとしては、フロンティア・ラボ社製のキャピラリーカラム「Ｕｌｔｒａ Ａｌｌｏｙ+−５（ＭＳ／ＨＴ）」（５％ジフェニル９５％ジメチルポリシロキサン、長さ＝３０ｍ、内径＝０．２５ｍｍ、フィルム厚さ＝０．２５μｍ）が挙げられる。また、前記質量分析計としては、（株）島津製作所製の商品名「ＱＰ２０１０シリーズ」などが挙げられる。 As the separation column, a capillary column “Ultra Alloy + -5 (MS / HT)” manufactured by Frontier Laboratories (5% diphenyl 95% dimethylpolysiloxane, length = 30 m, inner diameter = 0.25 mm, film thickness = 0.25 μm). Examples of the mass spectrometer include trade name “QP2010 series” manufactured by Shimadzu Corporation.
前記定量工程は、分析工程で検出された標準試料に由来するピークのピーク面積と定量対象成分に由来するピークのピーク面積との比に基づいて定量する工程である。ここで、熱分解ガスクロマトグラフ質量分析で得られたクロマトグラムのピーク面積は、通常の場合、成分の含有量を示すことから、濃度が既知の標準試料および定量対象成分に由来するピーク面積を比較することで、溶媒抽出液中の対象成分を定量することができる。さらに、抽出工程における抽出効率を考慮することで、ゴム組成物中の対象成分を定量することができる。 The quantification step is a step of quantifying based on a ratio between the peak area of the peak derived from the standard sample detected in the analysis step and the peak area of the peak derived from the component to be quantified. Here, the peak area of the chromatogram obtained by pyrolysis gas chromatograph mass spectrometry usually indicates the content of the component, so the peak areas derived from standard samples with known concentrations and the components to be quantified are compared. By doing so, the target component in the solvent extract can be quantified. Furthermore, the target component in the rubber composition can be quantified by considering the extraction efficiency in the extraction step.
本発明の定量方法によれば、微量しか含有していない成分をも定量することができる。具体的には、ゴム組成物中の含有量が０．１質量％以下の成分を定量することができる。 According to the quantification method of the present invention, a component containing only a trace amount can be quantified. Specifically, the component having a content of 0.1% by mass or less in the rubber composition can be quantified.
本発明を実施例に基づいて説明するが、本発明は実施例のみに限定されるものではない。 The present invention will be described based on examples, but the present invention is not limited to the examples.
以下に実施例において用いた各種薬品をまとめて示す。
ＮＲ：ＴＳＲ２０
しゃっかい剤：大内新興化学工業（株）製のノクタイザーＳＤ（有効成分（Ｎ−フェニルベンズアミド）を２５％含有）
カーボンブラック：三菱化学（株）製のダイアブラックＬＨ（Ｎ３２６）
老化防止剤：大内新興化学工業（株）製のノクラック２２４（２，２，４−トリメチル−１，２−ジヒドロキノリン重合体）
酸化亜鉛：東邦亜鉛（株）製の銀嶺Ｒ
オイル：出光興産（株）製のダイアナプロセスオイルＰＡ３２
ステアリン酸コバルト：大日本インキ化学工業（株）製のｃｏｓｔ−Ｆ（コバルト含有量：９．５質量％）
硫黄：鶴見化学工業（株）製の５％オイル処理粉末硫黄（オイル分５質量％含む可溶性硫黄）
加硫促進剤：大内新興化学工業（株）製のノクセラーＤＺ（ＤＣＢＳ）
The various chemicals used in the examples are summarized below.
NR: TSR20
Shaking agent: Nokutizer SD manufactured by Ouchi Shinsei Chemical Industry Co., Ltd. (containing 25% active ingredient (N-phenylbenzamide))
Carbon black: Dia Black LH (N326) manufactured by Mitsubishi Chemical Corporation
Anti-aging agent: NOCRACK 224 (2,2,4-trimethyl-1,2-dihydroquinoline polymer) manufactured by Ouchi Shinsei Chemical Co., Ltd.
Zinc oxide: Silver candy R made by Toho Zinc Co., Ltd.
Oil: Diana Process Oil PA32 manufactured by Idemitsu Kosan Co., Ltd.
Cobalt stearate: cost-F (cobalt content: 9.5% by mass) manufactured by Dainippon Ink & Chemicals, Inc.
Sulfur: 5% oil-treated powder sulfur manufactured by Tsurumi Chemical Co., Ltd. (soluble sulfur containing 5% oil content)
Vulcanization accelerator: Noxeller DZ (DCBS) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
ゴム組成物１〜３の調製
表１に示す配合内容に従い、上記各種薬品（硫黄および加硫促進剤を除く）を、神戸製鋼（株）製の１．７Ｌバンバリーミキサーにて混練りし、混練り物を得た。得られた混練り物に、硫黄および加硫促進剤を添加し、オープンロールを用いて練り込み、未加硫ゴム組成物を得た。得られた未加硫ゴム組成物を加硫しゴム組成物１〜３を得た。
Preparation of
ゴム組成物１〜３を２００μｇ±１０μｇの範囲内で精秤した。これに、５０μｇ／ｍｌのジベンゾチオフェン（標準試料）を含むアセトンを、ゴム組成物試料（ｍｇ）に対する抽出溶媒量（ｍｌ）が１００ｍｇ／ｍｌとなるように加え、２４時間室温（２３℃）で静置することで抽出工程を行った。抽出液をパスツールピペットにより回収し、減圧下でアセトンを留去させて、溶媒抽出物を得た。
The
得られた各溶媒抽出物を、熱分解ガスクロマトグラフ質量分析計により分析することで各ゴム組成物のガスクロマトグラムを得た（図１〜３）。参考例としてしゃっかい剤のみを熱分解ガスクロマトグラフ質量分析計により分析してガスクロマトグラムを得た（図４）。ゴム組成物２および３のガスクロマトグラムから、しゃっかい剤の有効成分である「Ｎ−フェニルベンズアミド」に由来するピークのピーク面積、およびジベンゾチオフェン（標準試料）に由来するピークのピーク面積を算出し、標準試料のピーク面積に対するしゃっかい剤のピーク面積（標準比）をｎ＝３で求めた。さらに、標準比のバラツキ（ＲＳＤ）を算出した。結果を表２に示す。
The obtained solvent extracts were analyzed by a pyrolysis gas chromatograph mass spectrometer to obtain gas chromatograms of the respective rubber compositions (FIGS. 1 to 3). As a reference example, only the masticant was analyzed by a pyrolysis gas chromatograph mass spectrometer to obtain a gas chromatogram (FIG. 4). From the gas chromatograms of
ＧＣＭＳ装置および測定条件は、以下の通りである。
ガスクロマトグラフ：（株）島津製作所製の「ＧＣＭＳ−ＱＰ２０１０」
熱分解装置：Ｆｒｏｎｔｉｅｒ Ｌａｂ社製の「ＰＹ−２０２０ｉＤ」
分離カラム：Ｆｒｏｎｔｉｅｒ Ｌａｂ社製の「Ｕｌｔｒａ ＡＬＬＯＹ+−５（ＭＳ／ＨＴ）」（５％ジフェニル９５％ジメチルポリシロキサン、長さ３０ｍ、内径０．２５ｍｍ、膜厚０．２５μｍ）
熱分解温度：５５０℃
試料注入部温度：３００℃
オーブン温度：４０℃／３ｍｉｎ−（昇温速度８℃／ｍｉｎ）−３００℃／４．５ｍｉｎ
The GCMS apparatus and measurement conditions are as follows.
Gas chromatograph: “GCMS-QP2010” manufactured by Shimadzu Corporation
Thermal decomposition apparatus: “PY-2020iD” manufactured by Frontier Lab
Separation column: “Ultra ALLOY + −5 (MS / HT)” manufactured by Frontier Lab (5% diphenyl 95% dimethylpolysiloxane, length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm)
Thermal decomposition temperature: 550 ° C
Sample injection part temperature: 300 ° C
Oven temperature: 40 ° C./3 min- (temperature increase rate 8 ° C./min)-300° C./4.5 min
表２の結果より、ゴム組成物２および３の標準比としゃっかい剤有効成分の濃度とが比例関係にあることから、標準試料を含むゴム組成物の溶媒抽出物を熱分解ガスクロマトグラフ質量分析計（ＧＣＭＳ）により分析することを特徴とし、得られたクロマトグラムにおける標準試料に由来するピークのピーク面積と定量対象成分に由来するピークのピーク面積との比に基づいて定量する本発明の定量方法によれば、微量しか含有していない成分をも定量することができることがわかる。
From the results in Table 2, since the standard ratio of
Claims (2)
標準試料を含むゴム組成物の溶媒抽出物を熱分解ガスクロマトグラフ質量分析計により分析して得られたクロマトグラムにおける標準試料に由来するピークのピーク面積と定量対象成分に由来するピークのピーク面積との比に基づいて定量する定量方法。 A method for quantifying ingredients in a rubber composition,
The peak area of the peak derived from the standard sample and the peak area derived from the component to be quantified in the chromatogram obtained by analyzing the solvent extract of the rubber composition containing the standard sample with a pyrolysis gas chromatograph mass spectrometer Quantification method based on the ratio of
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