JP2017194426A - Agarwood quality evaluation method - Google Patents
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- 241000271309 Aquilaria crassna Species 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000013441 quality evaluation Methods 0.000 title claims abstract description 22
- 238000004566 IR spectroscopy Methods 0.000 claims abstract description 8
- 238000010521 absorption reaction Methods 0.000 claims abstract description 7
- 230000005540 biological transmission Effects 0.000 claims abstract description 7
- 238000012844 infrared spectroscopy analysis Methods 0.000 claims description 11
- 238000004458 analytical method Methods 0.000 abstract description 19
- 238000011156 evaluation Methods 0.000 abstract description 17
- 230000001953 sensory effect Effects 0.000 abstract description 11
- 230000006378 damage Effects 0.000 abstract description 6
- 238000009658 destructive testing Methods 0.000 abstract 1
- 238000000862 absorption spectrum Methods 0.000 description 31
- 238000001228 spectrum Methods 0.000 description 19
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 230000003595 spectral effect Effects 0.000 description 7
- 239000003205 fragrance Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 230000001066 destructive effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 229920001817 Agar Polymers 0.000 description 4
- 239000008272 agar Substances 0.000 description 4
- 230000008786 sensory perception of smell Effects 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- ZZIZZTHXZRDOFM-XFULWGLBSA-N tamsulosin hydrochloride Chemical compound [H+].[Cl-].CCOC1=CC=CC=C1OCCN[C@H](C)CC1=CC=C(OC)C(S(N)(=O)=O)=C1 ZZIZZTHXZRDOFM-XFULWGLBSA-N 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 241000984061 Aquilaria Species 0.000 description 2
- 235000019568 aromas Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000015541 sensory perception of touch Effects 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 1
- 206010027146 Melanoderma Diseases 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000221035 Santalaceae Species 0.000 description 1
- 235000008632 Santalum album Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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Abstract
Description
本発明は、沈香の品質評価方法に関し、機器分析により沈香の品質を評価する。中でも、沈香の中でも最高品質である伽羅を特に見分けるための品質評価方法に関する。 The present invention relates to a method for evaluating agarwood quality, and evaluates the quality of agarwood by instrumental analysis. In particular, the present invention relates to a quality evaluation method for distinguishing mandala, which is the highest quality among agarwood.
沈香とは、アクイラリア（Ａｑｕｉｌａｒｉａ）属の材、特にその辺材の材質中に黒色の樹脂が沈着した香木であり、灰褐色〜黒褐色を呈し、所々に穴や溝を有するものもある。沈香は樹脂に富む部分は光沢のある黒点を有し、質は固く重い。また、僅かな香気があり、薫べると芳香を発する（非特許文献１）。 Agarwood is a fragrant tree in which a black resin is deposited in the material of the genus Aquilaria, particularly its sapwood, and has a grayish brown to dark brown color, and some have holes and grooves. Agarwood has a glossy black spot in the resin-rich part, and the quality is hard and heavy. In addition, there is a slight fragrance, and aroma is produced when it is burned (Non-patent Document 1).
アクイラリア属は東南アジアに多く生息し、中でもベトナムやラオス、インドネシアに多く見られる。材質中に樹脂が沈着するためには落雷等の外傷や虫食い等、何らかの衝撃が必要とされるが、その詳細は明らかになっていない。
また沈香は、白檀や松等、樹齢を重ねると必ず心材に油が溜まるものとは異なり、必ずしも樹脂が沈着するものではないことから、非常に貴重な香木資源である。
The genus Aquilaria is abundant in Southeast Asia, especially in Vietnam, Laos and Indonesia. In order for the resin to deposit in the material, some kind of impact such as lightning strikes and insect damage is required, but the details are not clear.
In addition, agarwood is a very valuable fragrance resource, such as sandalwood, pine, and the like, which does not necessarily deposit resin, unlike oil that accumulates in the heartwood whenever it grows old.
沈香とひと口に言っても、その樹脂の種類や量は様々であり、その品質は様々である。沈香の中でも最高品質のものは伽羅（きゃら）と呼ばれ、非常に貴重である。
ことに近年は、沈香の限りある資源の貴重さから、財産的価値を見出す場合も多く、品質評価や真贋鑑定のニーズが強い。
To say agarwood, there are various kinds and amounts of resin, and the quality is various. The highest quality of agarwood is called mandala and is very valuable.
In particular, in recent years, there are many cases where property value is found due to the preciousness of limited agarwood resources, and there is a strong need for quality evaluation and authenticity assessment.
一方、沈香は天然物であり、香木の種類、生育条件、樹齢や、樹脂沈着の要因、気象条件等、様々な要因が絡みあって沈香が得られることから、完全に同じ沈香は存在しないと言えるほどである。そのため、伽羅、沈香、人為的な沈香、偽物の沈香等と言った品質評価や真贋鑑定に際しての科学的分析手段による類型化は非常に困難であり、従来は熟練した鑑定者がその品質評価を担ってきた。 On the other hand, agarwood is a natural product, and since agarwood can be obtained by various factors such as the type of aroma tree, growth conditions, tree age, resin deposition factors, weather conditions, etc., there is no completely the same agarwood. I can say that. For this reason, it is very difficult to classify by qualitative evaluation such as mandala, agarwood, artificial agarwood, counterfeit agarwood, etc. and scientific analysis methods for authenticity assessment. I have been carrying it.
鑑定者による品質評価では、見た目（視覚）や、薫べた際の香り（嗅覚）、手触りや重み（触覚）等の五感を用いた官能評価が行われる。特に嗅覚を用いた評価においては、実際に沈香を加熱する必要があり、評価に用いた沈香は燃え尽きてしまう破壊試験となる。 In the quality evaluation by the appraiser, sensory evaluation using the five senses such as appearance (sight), scent when smelling (olfaction), touch and weight (tactile sense) is performed. In particular, in the evaluation using the sense of smell, it is necessary to actually heat the agarwood, and the agarwood used for the evaluation is a destructive test that burns out.
一方で、沈香の濫獲等により資源そのものの数が激減し、沈香、特に伽羅は現在非常に入手が困難である。 On the other hand, the abundance of agarwood has drastically reduced the number of resources, and agarwood, especially mandala, is currently very difficult to obtain.
本発明は上記実情に鑑みてなされたものであり、破壊試験、かつ熟練した技術が求められる鑑定者による官能評価を補助し、より確実な鑑定結果とするために、科学的分析技術として機器分析による新たな沈香の品質評価方法を提供することを目的とする。また、当該機器分析において、試料の破壊量をなくす（非破壊）又は極小にした新たな沈香の品質評価方法を提供することもさらなる目的とする。 The present invention has been made in view of the above-mentioned circumstances, and assists sensory evaluation by appraisers who require destructive tests and skilled techniques, and in order to obtain more reliable appraisal results, it is instrumental analysis as a scientific analysis technique. The purpose is to provide a new method for evaluating the quality of agarwood. Another object of the present invention is to provide a new agarwood quality evaluation method in which the amount of sample destruction is eliminated (non-destructive) or minimized in the instrumental analysis.
本発明者らは、科学的分析技術における機器分析の一つである赤外分光分析を選択し、該分析により得られたスペクトルデータを比較、解析することによって、複数種の沈香又は偽物の沈香を類型化できることを見出し、本発明を完成するに至った。
すなわち本発明は、上記課題を解決するものであり、下記［１］〜［５］に関するものである。
［１］ 中赤外又は熱赤外の赤外分光分析を用いて、沈香の１８００〜９００ｃｍ−１の領域における赤外吸収強度又は赤外透過強度を測定することを特徴とする沈香の品質評価方法。
［２］ 前記赤外分光分析が中赤外を用いたＡＴＲ法により行われる、前記［１］に記載の沈香の品質評価方法。
［３］ 中赤外又は熱赤外の赤外分光分析を用いて、さらに沈香の４０００〜１８００ｃｍ−１の領域における赤外吸収強度又は赤外透過強度を測定し、
１６６０〜１５９０ｃｍ−１の領域に二股に分かれた２つのピークが存在し、かつ
４０００〜９００ｃｍ−１の全領域中において、前記二股に分かれた２つのピークのうちピーク強度が高い方のピークよりもピーク強度が高いピークが存在しない、又は、３つ以下存在する、前記［１］又は［２］に記載の沈香の品質評価方法。
［４］ ４０００〜９００ｃｍ−１の全領域中に１０３０〜１０２８ｃｍ−１の領域におけるピークよりもピーク強度が高いピークが４つ以上存在する、又は、１０３０〜１０２８ｃｍ−１の領域にピークが存在しない、前記［３］に記載の沈香の品質評価方法。
［５］ ４０００〜９００ｃｍ−１の全領域中、１６４０〜１６３０ｃｍ−１の領域にピーク強度が最も大きなピークが存在する、前記［３］又は［４］に記載の沈香の品質評価方法。
The present inventors select infrared spectroscopic analysis, which is one of instrumental analysis in scientific analysis technology, and compare and analyze spectral data obtained by the analysis, whereby a plurality of types of agarwood or fake agarwood. Has been found to be typified, and the present invention has been completed.
That is, this invention solves the said subject and relates to following [1]-[5].
[1] Quality evaluation of agarwood characterized by measuring infrared absorption intensity or infrared transmission intensity in the region of 1800 to 900 cm −1 of agarwood using infrared spectroscopy of mid-infrared or thermal infrared. Method.
[2] The quality evaluation method for agarwood according to [1], wherein the infrared spectroscopic analysis is performed by an ATR method using mid-infrared.
[3] Using infrared spectroscopy of mid-infrared or thermal infrared, further measure infrared absorption intensity or infrared transmission intensity in the region of 4000-1800 cm −1 of agarwood,
There are two peaks divided into two forks in the region of 1660 to 1590 cm −1 , and in the whole region of 4000 to 900 cm −1 , the peak having the higher peak intensity of the two peaks divided into two forks The method for evaluating quality of agarwood according to [1] or [2], wherein a peak having a high peak intensity does not exist, or 3 or less exist.
[4] There are four or more peaks having a peak intensity higher than the peak in the region of 1030 to 1028 cm −1 in the entire region of 4000 to 900 cm −1 , or no peak in the region of 1030 to 1028 cm −1. The quality evaluation method of agarwood as described in said [3].
[5] The quality evaluation method for agarwood according to [3] or [4], wherein a peak having the highest peak intensity exists in a region of 1640 to 1630 cm −1 in a whole region of 4000 to 900 cm −1 .
本発明に係る品質評価方法は、沈香の科学的センシングによる評価が可能であるという世界初の知見をもたらすものであり、破壊量が極小又は非破壊で沈香の品質や真贋を評価、判断することができる。さらには、鑑定者による鑑定技術を科学技術による評価手法で補助することにより、鑑定結果に客観性を与え、より確実なものとすることができる。本発明により、今後、沈香を始めとする香木の評価に共通の鑑定プラットフォーム基板技術としての発展が期待できる。 The quality evaluation method according to the present invention brings the world's first knowledge that agarwood can be evaluated by scientific sensing, and evaluates and judges the quality and authenticity of agarwood with minimal or non-destructive amount of destruction. Can do. Furthermore, by assisting the appraisal technique by the appraiser with an evaluation method based on science and technology, the appraisal result can be made objective and more reliable. In the future, the present invention can be expected to develop as an appraisal platform substrate technology common to the evaluation of aromas including agarwood.
以下、本発明を詳細に説明するが、本発明は以下の実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲において、任意に変形して実施することができる。
本明細書において数値範囲を示す「〜」とは、その前後に記載された数値を下限値及び上限値として含む意味で使用される。
Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be arbitrarily modified without departing from the gist of the present invention.
In the present specification, “to” indicating a numerical range is used in a sense including numerical values described before and after the numerical value as a lower limit value and an upper limit value.
本来、赤外分光分析は、分子の振動や回転の状態を変化させるのに必要なエネルギーを与え（赤外光を照射し）、透過又は反射した光を測定する分析方法である。得られた赤外吸収スペクトルは主として分子の固有振動数に基づくため、分子が異なれば必ずスペクトルも異なる。そのため、物質の構造解析（同定）や定性分析、定量分析等を行うことができる。
一方、沈香は木材に樹脂が沈着した香木であることから、赤外分光分析により得られるスペクトルは木材や樹脂の種類によって様々であり収束しないものと考えられていた。しかしながら本発明では、鋭意検討の結果、沈香の品質によって該スペクトルを類型化することが可能となった。
Originally, infrared spectroscopic analysis is an analysis method in which energy necessary for changing the vibrational and rotational states of molecules is applied (irradiated with infrared light) and transmitted or reflected light is measured. Since the obtained infrared absorption spectrum is mainly based on the natural frequency of the molecule, the spectrum is always different for different molecules. Therefore, structural analysis (identification), qualitative analysis, quantitative analysis, etc. of a substance can be performed.
On the other hand, since agarwood is a fragrant tree in which resin is deposited on wood, the spectrum obtained by infrared spectroscopic analysis varies depending on the type of wood and resin, and is considered not to converge. However, in the present invention, as a result of intensive studies, it has become possible to classify the spectrum according to the quality of agarwood.
すなわち、本発明に係る沈香の品質評価方法は、中赤外又は熱赤外の赤外分光分析（ＩＲ）を用いて、沈香の１８００〜９００ｃｍ−１の領域における赤外吸収強度又は赤外透過強度を測定することを特徴とする。
かかる方法により、試料となる沈香を非破壊で、又は極小の破壊量で沈香の品質を評価することができる。また、機器を用いた分析であることから、評価結果に客観性を与え、一般化することができる。なお、本明細書において、沈香の品質の評価とは、沈香の真贋の評価も含む意味である。
That is, the quality evaluation method of agarwood according to the present invention uses infrared absorption analysis or infrared transmission in the region of 1800 to 900 cm −1 of agarwood using infrared spectroscopy (IR) of mid-infrared or thermal infrared. It is characterized by measuring strength.
By such a method, it is possible to evaluate the quality of agarwood without breaking the agarwood as a sample or with a minimal amount of destruction. Moreover, since the analysis is performed using an instrument, the evaluation result can be provided with objectivity and generalized. In the present specification, the evaluation of agarwood quality includes the evaluation of agarwood authenticity.
赤外分光分析（ＩＲ）における赤外光は中赤外又は熱赤外であればよいが、本明細書において、中赤外とは波長２．５〜２５μｍの波長域の光を意味し、熱赤外とは波長２５μｍ〜１ｍｍの波長域の光を意味する。中でも分子の振動の基本周波数を計測する観点から中赤外を用いたＩＲが好ましい。
また、赤外分光分析の中でも、フーリエ変換赤外分光法（ＦＴ−ＩＲ）が好ましい。
Infrared light in infrared spectroscopic analysis (IR) may be mid-infrared or thermal infrared, but in this specification, mid-infrared means light in the wavelength range of 2.5 to 25 μm, Thermal infrared means light in the wavelength range of 25 μm to 1 mm. Among these, IR using mid-infrared is preferable from the viewpoint of measuring the fundamental frequency of molecular vibration.
Among infrared spectroscopic analyses, Fourier transform infrared spectroscopy (FT-IR) is preferable.
赤外分光分析において任意の測定法を用いることができ、透過法でも反射法でもよいが、試料を非破壊で測定できることからＡＴＲ（全反射）法がより好ましい。 Any measurement method can be used in the infrared spectroscopic analysis, and either a transmission method or a reflection method may be used. However, since the sample can be measured nondestructively, the ATR (total reflection) method is more preferable.
本発明においては、沈香の１８００〜９００ｃｍ−１の領域における赤外吸収スペクトルから沈香の品質を評価できるものであるが、より詳細なスペクトルの解析を行うために、測定領域を４０００〜９００ｃｍ−１とすることが好ましく、４０００〜６００ｃｍ−１とすることがより好ましい。 In the present invention, the quality of the agar can be evaluated from the infrared absorption spectrum in the 1800 to 900 cm −1 region of the agarwood. In order to analyze the spectrum in more detail, the measurement region is set to 4000 to 900 cm −1. It is preferable to set it as 4,000-600 cm < -1 >.
以下、沈香の赤外分光分析により得られるスペクトルについて、品質評価方法を具体的に述べる。
なお、本明細書における赤外吸収スペクトルは、ＴｈｅｒｍｏＦｉｓｈｅｒ ＳＣＩＥＮＴＩＦＩＣ社製のＮｉｃｏｌｅｔ ８７００ＦＴ−ＩＲのＦＴ−ＩＲ装置とＳｅｎｓＩＲ社製のＤｕｒａＳｃｏｐｅのＡＴＲアクセサリを用い、ＡＴＲ法により下記の条件で測定した場合のものである。得られるピークトップの波数の誤差は約±１ｃｍ−１である。
Hereinafter, a quality evaluation method will be specifically described for a spectrum obtained by infrared spectroscopic analysis of agarwood.
In addition, the infrared absorption spectrum in this specification is a thing when the FT-IR apparatus of Nicolet 8700FT-IR made by ThermoFisher SCIENTIFIC and the ATR accessory of DuraScope made by SensIR are measured by the ATR method under the following conditions. It is. The peak top wave number error obtained is about ± 1 cm −1 .
（試料調製）
試料となる沈香から、厚さ０．５ｍｍ程度、サイズ２〜３ｍｍ四方の破片を切り出した。
（測定条件）
・測定法：ＡＴＲ法
・光照射面積：直径１ｍｍ
・分解能：４ｃｍ−１
・スキャン回数：６４回
なお、本明細書内で示す赤外吸収スペクトル（反射率）のグラフにおいて、反射率の値が急峻に下がっているところをピークと呼ぶ。ピークとして判定するか否かの詳細な判定方法については後述するが、反射率の微分と演算式とから判定される。スペクトルにおいてピークが見られるということは、その波数域で物質の吸収が見られることを表す。
また、本明細書においてはピーク強度の補正は行っていないが、ＡＴＲ法においては、ＡＴＲ結晶界面のもぐり込み深さが波長によって異なる。波数が低いほど（波長が長いほど）当該もぐり込み深さが大きくなるので、必要に応じて、ピーク強度が増大する傾向があることを勘案してスペクトルの解析を行う。
(Sample preparation)
From the agarwood used as a sample, a piece having a thickness of about 0.5 mm and a size of 2 to 3 mm square was cut out.
(Measurement condition)
・ Measurement method: ATR method ・ Light irradiation area: 1mm in diameter
・ Resolution: 4cm -1
-Number of scans: 64 times In the graph of the infrared absorption spectrum (reflectance) shown in this specification, a point where the reflectance value is sharply lowered is called a peak. Although a detailed determination method for determining whether or not to determine the peak will be described later, it is determined from the differential of the reflectance and the arithmetic expression. The fact that a peak is observed in the spectrum means that absorption of the substance is observed in the wave number region.
In this specification, the peak intensity is not corrected, but in the ATR method, the penetration depth of the ATR crystal interface varies depending on the wavelength. The lower the wave number (the longer the wavelength), the larger the penetration depth, so that the spectrum analysis is performed considering that the peak intensity tends to increase as necessary.
顕微−透過法で赤外分光分析を行う際の測定条件は上記と同様であり、上記とほぼ同様のスペクトルが得られる。 The measurement conditions for performing infrared spectroscopic analysis by the microscopic-transmission method are the same as described above, and a spectrum substantially similar to the above is obtained.
得られた赤外吸収スペクトル（反射率）のグラフの微分スペクトルと演算式から、ピークとするか否かの判定を行う。
まず、赤外吸収スペクトル（反射率）の微分スペクトルにおいて、長波数側から見た際に正から負の方向にゼロをまたぐものをピーク候補として検出する。なお、微分スペクトルの例として、伽羅の赤外吸収スペクトルを示す図１の微分スペクトルを図６に、沈香の赤外吸収スペクトルを示す図４の微分スペクトルを図７にそれぞれ示す。
From the differential spectrum of the graph of the obtained infrared absorption spectrum (reflectance) and the arithmetic expression, it is determined whether or not to make a peak.
First, in the differential spectrum of the infrared absorption spectrum (reflectance), the one that crosses zero in the positive to negative direction when viewed from the long wave number side is detected as a peak candidate. As an example of the differential spectrum, FIG. 6 shows the differential spectrum of FIG. 1 showing the infrared absorption spectrum of Mandala, and FIG. 7 shows the differential spectrum of FIG. 4 showing the infrared absorption spectrum of agarwood.
ピークの判定はＯＭＮＩＣ ｖｅｒ．６．２を用いて、得られた赤外吸収スペクトル（反射率）のグラフのデータを読み込み、次いで、ピーク検出機能を選択し、図９に示したソフトウェア上の画面において閾値及び感度を調整し、閾値設定ラインと感度設定を行うことにより、上記で検出されたピーク候補からピークとして判定するものを自動検出する。なお、上記ソフトウェアを用いたピークの自動検出は、下記演算式を用いて判定されるものである。
Ａｂｓ Ｓｅｎｓ＝０．５＊（Ｍａｘ−ｍｉｎ）＊ｅｘｐ（−０．０１＊ｓｅｎｓｉｔｉｖｉｔｙ）
上記演算式中、「ｓｅｎｓｉｔｉｖｉｔｙ」は０〜１００の範囲で任意で設定できるものであるが、本明細書においては、試料間で差異が出ないように７０に固定する。
なお、得られたスペクトルによっては、スペクトル分析おいて、手動でピーク検出を行うなど、適宜調整を行ってもよい。
The peak is determined by OMNIC ver. Use 6.2 to read the obtained infrared absorption spectrum (reflectance) graph data, then select the peak detection function and adjust the threshold and sensitivity on the software screen shown in FIG. By performing the threshold setting line and sensitivity setting, what is determined as a peak from the peak candidates detected above is automatically detected. The automatic peak detection using the software is determined using the following arithmetic expression.
Abs Sens = 0.5 * (Max-min) * exp (−0.01 * sensitivity)
In the above arithmetic expression, “sensitivity” can be arbitrarily set in the range of 0 to 100, but in this specification, it is fixed at 70 so that there is no difference between samples.
Depending on the obtained spectrum, adjustment may be made as appropriate, such as performing peak detection manually in spectrum analysis.
沈香の真贋は、４０００〜９００ｃｍ−１の領域における赤外吸収スペクトルから判断することができる。具体的には、赤外吸収スペクトルにおいて下記（ａ）及び（ｂ）に該当すれば、本物の沈香であると判断することができる。
（ａ）１６６０〜１５９０ｃｍ−１の領域に二股に分かれた２つのピークが存在する。
（ｂ）前記（ａ）における二股に分かれた２つのピークのうちピーク強度が高い方のピークよりもピーク強度が高いピークが存在しない、又は、３つ以下存在する。
The authenticity of agarwood can be judged from the infrared absorption spectrum in the region of 4000 to 900 cm −1 . Specifically, if the following (a) and (b) are satisfied in the infrared absorption spectrum, it can be determined that the agar is genuine.
(A) Two peaks divided into two forks exist in the region of 1660 to 1590 cm −1 .
(B) Of the two peaks divided into two forks in (a), there is no peak with a peak intensity higher than the peak with the higher peak intensity, or there are three or less peaks.
例えば伽羅の赤外吸収スペクトルを示す図１においては、４０００〜９００ｃｍ−１の領域中、１６６０〜１５９０ｃｍ−１の領域において、１６３３．６５ｃｍ−１と１６０２．４５ｃｍ−１に二股に分かれた２つのピークが存在し、１６３３．６５ｃｍ−１のピークよりもピーク強度が高いピークは存在しない。
また、沈香の赤外吸収スペクトルを示す図４においては、４０００〜９００ｃｍ−１の領域中、１６６０〜１５９０ｃｍ−１の領域において、１６５６．０４ｃｍ−１と１５９８．５６ｃｍ−１に二股に分かれた２つのピークが存在し、１６５６．０４ｃｍ−１のピークよりもピーク強度が高いピークは、３３５２．３９ｃｍ−１、２９２３．２９ｃｍ−１及び１０３０．３１ｃｍ−１に３つ存在する。
For example, in FIG. 1 shows an infrared absorption spectrum of a character, in the region of 4000～900Cm -1, in the region of 1660~1590cm -1, 2 two bifurcated to 1633.65Cm -1 and 1602.45Cm -1 There is a peak, and no peak has a higher peak intensity than the peak at 1633.65 cm −1 .
Further, in FIG. 4 shows an infrared absorption spectrum of agarwood, in the region of 4000～900Cm -1, in the region of 1660～1590Cm -1, bifurcated into 1656.04Cm -1 and 1598.56cm -1 2 There are two peaks, and three peaks with higher peak intensity than the peak at 1656.04 cm −1 are present at 3352.39 cm −1 , 2923.29 cm −1 and 1030.31 cm −1 .
一方、沈香の偽物の赤外吸収スペクトルを示す図５においては、４０００〜９００ｃｍ−１の領域中、１６６０〜１５９０ｃｍ−１の領域において、比較的ブロードではあるものの、１６３４．８０ｃｍ−１と１５９７．３４ｃｍ−１に二股に分かれた２つのピークが存在し、１６３４．８０ｃｍ−１のピークよりもピーク強度が高いピークは、３３２９．２６ｃｍ−１、２９５１．８４ｃｍ−１、２９２１．９９ｃｍ−１、２８５２．７３ｃｍ−１及び１０２９．６８ｃｍ−１に５つ存在する。 On the other hand, in FIG. 5 shows an infrared absorption spectrum of agarwood fake, in the region of 4000～900Cm -1, in the region of 1660～1590Cm -1, although relatively broad is in a 1634.80cm -1 1597. there are two peaks bifurcated to 34cm -1, peak peak intensity is higher than the peak of 1634.80Cm -1 is, 3329.26cm -1, 2951.84cm -1, 2921.99cm -1, 2852 There are five at .73 cm −1 and 1029.68 cm −1 .
なお、本物の沈香であっても、沈香の種類によっては前記（ａ）及び／又は（ｂ）に該当しない場合がある。
また、偽物の沈香のうち、沈香となる木を用いて、そこに人工的に樹脂を注入し、さらに金属等を挿入して重みを持たせたものは、木そのものが沈香となる木であることから、赤外吸収スペクトルが本物の沈香のスペクトルと似る場合がある。その場合には、金属の有無を検出する等、他の方法により真贋を判定することが可能である。
In addition, even if it is a genuine agarwood, it may not correspond to said (a) and / or (b) depending on the kind of agarwood.
Moreover, among the fake agarwood, the one that is artificially infused with a tree that becomes agarwood and that is given weight by inserting metal or the like is a tree that is itself agarwood. Therefore, the infrared absorption spectrum may resemble the spectrum of real agarwood. In that case, authenticity can be determined by other methods such as detecting the presence or absence of metal.
前記（ａ）について、１６６０〜１５９０ｃｍ−１の領域に二股に分かれた２つのピークがブロードとなっており、明確にピークと認識できない場合がある。この場合、沈香は偽物であることが多い。
また、１６６０〜１５９０ｃｍ−１の領域における２つのピークの反射率（ピーク強度）の差が１％以上で、かつ、高波数側のピークの方が大きい場合に伽羅であることが多い傾向がある。一方、偽物の沈香の場合は、当該２つのピークの反射率（ピーク強度）の差が１％未満程度であることが多い。例えば図５に示す偽物の沈香の場合、１６３４．８０ｃｍ−１における反射率は９１．５％であり、１５９７．３４ｃｍ−１における反射率は９１．７％であることから、その差は約０．２％と、１％未満である。
In the case of (a), two peaks divided into two forks in the region of 1660 to 1590 cm −1 are broad and may not be clearly recognized as peaks. In this case, agarwood is often a fake.
In addition, when the difference in reflectance (peak intensity) between two peaks in the region of 1660 to 1590 cm −1 is 1% or more and the peak on the high wave number side is larger, it tends to be mandala. . On the other hand, in the case of fake agarwood, the difference in reflectance (peak intensity) between the two peaks is often less than about 1%. For example, in the case of fake agarwood shown in FIG. 5, the reflectance at 1634.80 cm −1 is 91.5% and the reflectance at 1597.34 cm −1 is 91.7%. .2% and less than 1%.
前記（ａ）及び（ｂ）に該当する沈香に対し、赤外吸収スペクトルにおいて下記（ｃ）及び／又は（ｄ）により、その品質を評価することができる。なお、下記（ｃ）及び（ｄ）の少なくともいずれか一方に該当すれば伽羅である可能性が高い。なお参考として、図８に、特徴（ａ）〜（ｄ）を用いた本発明に係る沈香の評価方法を示すフロー図を示す。
（ｃ）４０００〜９００ｃｍ−１の全領域中に１０３０〜１０２８ｃｍ−１の領域におけるピークよりもピーク強度が高いピークが４つ以上存在する、又は、１０３０〜１０２８ｃｍ−１の領域にピークが存在しない。
（ｄ）４０００〜９００ｃｍ−１の全領域中、１６４０〜１６３０ｃｍ−１の領域にピーク強度が最も大きなピークが存在する。
The quality of the incense corresponding to the above (a) and (b) can be evaluated by the following (c) and / or (d) in the infrared absorption spectrum. In addition, if it corresponds to at least any one of following (c) and (d), possibility of being a mandala is high. For reference, FIG. 8 is a flowchart showing the agarwood evaluation method according to the present invention using the features (a) to (d).
(C) There are four or more peaks having a peak intensity higher than the peak in the region of 1030 to 1028 cm −1 in the entire region of 4000 to 900 cm −1 , or no peak in the region of 1030 to 1028 cm −1. .
(D) A peak having the highest peak intensity exists in the region of 1640 to 1630 cm −1 in the entire region of 4000 to 900 cm −1 .
前記（ｃ）に関し、伽羅である図１、３の赤外吸収スペクトルでは、それぞれ１０２９．９４ｃｍ−１、１０２９．８３ｃｍ−１のピークよりもピーク強度が高いピークは４つ以上存在する。また、伽羅である図２の赤外吸収スペクトルでは、１０３０〜１０２８ｃｍ−１の領域にピークが存在しない。
一方、沈香である図４の赤外吸収スペクトルでは、１０３０．３１ｃｍ−１のピーク（誤差として１０３０〜１０２８ｃｍ−１の領域のピークと判断）よりもピーク強度が高いピークは２９２３．２９ｃｍ−１の１つのみである。
The respect (c), the infrared absorption spectrum of Figure 1 and 3 are Kyara, respectively 1029.94Cm -1, peak peak intensity is higher than the peak of 1029.83Cm -1 exist four or more. Moreover, in the infrared absorption spectrum of FIG. 2, which is a mandala, no peak exists in the region of 1030 to 1028 cm −1 .
On the other hand, in FIG. 4 is a agarwood In infrared absorption spectrum, the peak peak intensity is higher than the peak (determined as the peak area of 1030～1028Cm -1 as error) 1030.31Cm -1 is the 2923.29Cm -1 There is only one.
前記（ｄ）に関し、伽羅である図１〜３の赤外吸収スペクトルでは、それぞれ１６３３．６５ｃｍ−１、１６３６．４２ｃｍ−１、及び１６３４．９６ｃｍ−１に最も大きなピークが存在する。一方、沈香である図４の赤外吸収スペクトルでは２９２３．２９ｃｍ−１におけるピークが最も大きい。 The regard (d), the infrared absorption spectrum of FIG. 1-3 is a Kyara, respectively 1633.65cm -1, 1636.42cm -1, and the largest peak present in 1634.96cm -1. On the other hand, in the infrared absorption spectrum of FIG. 4 which is agarwood, the peak at 2923.29 cm −1 is the largest.
また、上記（ｃ）、（ｄ）の他に、伽羅が示す傾向として、下記（ｅ）、（ｆ）を挙げることができる。
（ｅ）前記（ａ）における二股に分かれた２つのピークが１６４０〜１６３０ｃｍ−１の領域と、１６０５〜１６００ｃｍ−１の領域に１つずつ存在する。
（ｆ）１５００〜１０００ｃｍ−１の領域において存在するピークが、シャープかつビジーに存在する。
In addition to the above (c) and (d), the following (e) and (f) can be cited as the tendency of the mandala.
(E) 2 peaks bifurcated in the (a) is present one and regions of 1640~1630cm -1, in the region of 1605~1600cm -1.
(F) A peak existing in the region of 1500 to 1000 cm −1 is sharp and busy.
上記（ｅ）について、沈香であって伽羅ではない図４の赤外吸収スペクトルでは、１６５６．０４ｃｍ−１と１５９８．５６ｃｍ−１にピークが存在しており、伽羅である図１〜３の赤外吸収スペクトルに比べて、二股に分かれた２つのピークが離れて存在している。 For the (e), in the infrared absorption spectrum of FIG. 4 was not Kyara by a agarwood, there are peaks 1656.04Cm -1 and 1598.56Cm -1, of Figures 1-3 are Kyara red Compared to the outer absorption spectrum, there are two peaks separated from each other.
上記（ｆ）について、ピークがシャープであること、及びビジーに（密に）存在することの定義を定めることは難しいが、複数の試料を相対的に見た際に、赤外吸収スペクトルのグラフの微分スペクトルにおける縦軸の絶対値（振れ幅）が大きいほどシャープであると言え、特定波数領域中に検出されるピークの数が多いほどビジーであると言える。
例えば、ＡＴＲ法によるスペクトルデータとその微分曲線を見比べると、伽羅（図１〜３及び図６参照）に比べて沈香（図４及び図７参照）は、１５００〜１０００ｃｍ−１の領域において検出されているピークがブロードになり、かつ密度も疎となっていることが分かる。
Regarding (f) above, it is difficult to define the definition that the peak is sharp and busy (densely), but when a plurality of samples are relatively viewed, the graph of the infrared absorption spectrum It can be said that the larger the absolute value (vibration width) of the vertical axis in the differential spectrum is, the sharper the signal is, and the more the number of peaks detected in the specific wave number region is, the more busy the signal is.
For example, comparing spectral data obtained by the ATR method with its differential curve, agarwood (see FIGS. 4 and 7) is detected in the region of 1500 to 1000 cm −1 compared to mandala (see FIGS. 1 to 3 and 6). It can be seen that the peak is broad and the density is sparse.
以下、実施例により本発明を具体的に説明する。ただし、本発明はこれらの実施例に限定されるものではない。
＜機器分析による品質評価：赤外分光分析−ＡＴＲ法＞
試料１〜５について、ＴｈｅｒｍｏＦｉｓｈｅｒ ＳＣＩＥＮＴＩＦＩＣ社製のＮｉｃｏｌｅｔ ８７００ＦＴ−ＩＲのＦＴ−ＩＲ装置とＳｅｎｓＩＲ社製のＤｕｒａＳｃｏｐｅのＡＴＲアクセサリを用いて、ＡＴＲ法により赤外吸収スペクトルを測定した。測定条件は下記に示したとおりである。
Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited to these examples.
<Quality evaluation by instrumental analysis: infrared spectroscopy-ATR method>
For samples 1 to 5, infrared absorption spectra were measured by the ATR method using a Nicolet 8700FT-IR FT-IR apparatus manufactured by ThermoFisher SCIENTIFIC and a DuraScope ATR accessory manufactured by SensIR. The measurement conditions are as shown below.
（試料調製）
試料である香木から、厚さ０．５ｍｍ程度、サイズ２〜３ｍｍ四方の破片を切り出した。なお、香木は色が均一ではなく濃淡があるが、色が濃い方が香木の特徴を有していると一般的にはされていることから、各試料のうち色の濃い部分を選択して試料の調製を行った。なお、香木は５種類用意し、試料１〜５とした。
(Sample preparation)
A piece having a thickness of about 0.5 mm and a size of 2 to 3 mm square was cut out from the sample wood. In addition, the fragrance is not uniform in color and has a light and shade, but it is generally said that the darker one has the characteristics of the fragrance, so select the dark part of each sample. Sample preparation was performed. In addition, five kinds of fragrance trees were prepared and used as samples 1 to 5.
（測定条件）
・測定法：ＡＴＲ法
・光照射面積：直径１ｍｍ
・測定範囲：４０００〜６５０ｃｍ−１
・分解能：４ｃｍ−１
・スキャン回数：６４回
ＴｈｅｒｍｏＦｉｓｈｅｒ ＳＣＩＥＮＴＩＦＩＣ社製のＦＴ−ＩＲ装置のソフトウェア（ＯＭＮＩＣ ｖｅｒ．６．２）を用い、得られたスペクトルデータから、先述した方法に基づいて、赤外吸収スペクトル（反射率）の微分スペクトルと演算式からピークを判定し検出した。なお、得られるピークトップの波数の誤差は±１ｃｍ−１である。
(Measurement condition)
・ Measurement method: ATR method ・ Light irradiation area: 1mm in diameter
Measurement range: 4000 to 650 cm −1
・ Resolution: 4cm -1
-Number of scans: 64 times Infrared absorption spectrum (reflectance) based on the above-described method from the obtained spectrum data using the FT-IR apparatus software (OMNIC ver. 6.2) manufactured by ThermoFisher SCIENTIFIC. The peak was determined and detected from the differential spectrum and the calculation formula. Note that the error of the wave number of the obtained peak top is ± 1 cm −1 .
得られた赤外吸収スペクトルから、下記（ａ）及び（ｂ）に該当するものを沈香又は伽羅とし、該当しないものを偽物の沈香とした。また、（ａ）及び（ｂ）に該当したもののうち下記（ｃ）及び（ｄ）の少なくともいずれか一方に該当したものを伽羅とした。以上により、伽羅、沈香、偽物の沈香の３種類に分類した。 From the obtained infrared absorption spectrum, those corresponding to the following (a) and (b) were set as agarwood or mandala, and those not applicable were set as fake agarwood. Moreover, the thing which corresponded to at least any one of following (c) and (d) among what corresponded to (a) and (b) was made into the mandala. Based on the above, it was classified into three types: mandala, agarwood, and fake agarwood.
（ａ）１６６０〜１５９０ｃｍ−１の領域に二股に分かれた２つのピークが存在する。
（ｂ）前記（ａ）における二股に分かれた２つのピークのうちピーク強度が高い方のピークよりもピーク強度が高いピークが存在しない、又は、３つ以下存在する。
（ｃ）４０００〜９００ｃｍ−１の全領域中に１０３０〜１０２８ｃｍ−１の領域におけるピークよりもピーク強度が高いピークが４つ以上存在する、又は、１０３０〜１０２８ｃｍ−１の領域にピークが存在しない。
（ｄ）４０００〜９００ｃｍ−１の全領域中、１６４０〜１６３０ｃｍ−１の領域にピーク強度が最も大きなピークが存在する。
(A) Two peaks divided into two forks exist in the region of 1660 to 1590 cm −1 .
(B) Of the two peaks divided into two forks in (a), there is no peak with a peak intensity higher than the peak with the higher peak intensity, or there are three or less peaks.
(C) There are four or more peaks having a peak intensity higher than the peak in the region of 1030 to 1028 cm −1 in the entire region of 4000 to 900 cm −1 , or no peak in the region of 1030 to 1028 cm −1. .
(D) A peak having the highest peak intensity exists in the region of 1640 to 1630 cm −1 in the entire region of 4000 to 900 cm −1 .
＜官能試験による品質評価＞
試料１〜５について、熟練した鑑定者による官能評価により沈香の真贋及び品質評価を行った。
官能評価は、見た目（視覚）や、薫べた際の香り（嗅覚）、手触りや重み（触覚）による総合判断を行った。嗅覚を用いた官能評価方法は以下のとおりである。
香炉に灰を入れ、火をつけた炭を前記灰の上にのせた。次いで前記炭が十分に熾っていることを確認したのち、炭の周りで熱くなった灰（約２００℃）の上に試料の極小片（約０．１ｇ）をのせて加熱した。試料から芳香する香りの種類や拡散性を確認した上で、鑑定者独自の評価基準に則り、伽羅、沈香、偽物の沈香の３種類に分類した。
<Quality evaluation by sensory test>
About samples 1-5, the authenticity and quality evaluation of agarwood were performed by sensory evaluation by a skilled appraiser.
For sensory evaluation, comprehensive judgment was made based on appearance (sight), scent when smelling (olfaction), touch and weight (tactile sense). The sensory evaluation method using olfaction is as follows.
Ash was placed in the incense burner, and a charcoal that was set on fire was placed on the ash. Next, after confirming that the charcoal was sufficiently burned, a small piece (about 0.1 g) of the sample was placed on the ash (about 200 ° C.) that became hot around the charcoal and heated. After confirming the type and diffusibility of the fragrance from the sample, it was classified into three types: mandala, agarwood, and counterfeit agarwood according to the appraiser's own evaluation criteria.
試料１〜５の赤外分光分析結果の赤外吸収スペクトルを図１〜５に、試料１及び４の赤外吸収スペクトルの微分曲線を図６及び７にそれぞれ示した。また、表１に赤外吸収スペクトル解析の結果及びそれらによる品質評価結果と、官能試験による品質評価結果を示した。 The infrared absorption spectra of the infrared spectroscopic analysis results of Samples 1 to 5 are shown in FIGS. 1 to 5, and the differential curves of the infrared absorption spectra of Samples 1 and 4 are shown in FIGS. 6 and 7, respectively. Table 1 shows the results of infrared absorption spectrum analysis, the quality evaluation results based on the results, and the quality evaluation results based on the sensory test.
その結果、試料１〜３は前記（ａ）〜（ｄ）のすべての特徴を有し、機器分析及び官能試験の結果、共に伽羅であると判定された。試料４は前記（ａ）及び（ｂ）の特徴を有し、（ｃ）及び（ｄ）のいずれの特徴も有さず、機器分析及び官能試験の結果、共に沈香であると判定された。試料５は前記（ｂ）の特徴を有さず、機器分析及び官能試験の結果、共に偽物の沈香であると判定された。 As a result, Samples 1 to 3 had all the characteristics (a) to (d), and were determined to be mandala as a result of instrumental analysis and sensory test. Sample 4 has the characteristics of (a) and (b) described above, and does not have any of the characteristics of (c) and (d). As a result of instrumental analysis and sensory test, both were determined to be agarwood. Sample 5 did not have the characteristics of (b), and was determined to be fake agarwood as a result of instrumental analysis and sensory test.
本発明に係る品質評価方法は、沈香の科学的センシングによる評価が可能であるという世界初の知見をもたらすものであり、破壊量が極小又は非破壊で沈香の品質や真贋を評価、判断することができる。そのため、鑑定者による鑑定技術と共に、当該科学技術による手法を用いることにより、鑑定に客観性を与え、より確実なものとすることができる。
さらには、沈香を始めとする香木の評価に共通の鑑定プラットフォーム基盤技術としての発展が期待でき、香木に関する科学的データや様々な知見を集積することで、鑑定ビジネスを視野に入れた新たなビジネスモデルの構築にもつながる可能性があることから、その技術的意義は極めて大きなものである。
The quality evaluation method according to the present invention brings the world's first knowledge that agarwood can be evaluated by scientific sensing, and evaluates and judges the quality and authenticity of agarwood with minimal or non-destructive amount of destruction. Can do. Therefore, by using the technique based on the science and technology together with the appraisal technique by the appraiser, the objectivity can be given to the appraisal and it can be made more reliable.
Furthermore, it can be expected to develop as a common appraisal platform technology for the evaluation of aromas such as agarwood, and by accumulating scientific data and various knowledge related to incense, a new business with a view to appraisal business The technical significance is extremely large because it may lead to model construction.
Claims (5)
１６６０〜１５９０ｃｍ−１の領域に二股に分かれた２つのピークが存在し、かつ
４０００〜９００ｃｍ−１の全領域中において、前記二股に分かれた２つのピークのうちピーク強度が高い方のピークよりもピーク強度が高いピークが存在しない、又は、３つ以下存在する、請求項１又は２に記載の沈香の品質評価方法。 Using infrared spectroscopy of mid-infrared or thermal infrared, further measure the infrared absorption intensity or infrared transmission intensity in the 4000-1800 cm −1 region of agarwood,
There are two peaks divided into two forks in the region of 1660 to 1590 cm −1 , and in the whole region of 4000 to 900 cm −1 , the peak having the higher peak intensity of the two peaks divided into two forks The method for evaluating the quality of agarwood according to claim 1 or 2, wherein there is no peak having a high peak intensity, or there are three or less peaks.
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| CN108802253A (en) * | 2017-12-11 | 2018-11-13 | 北京林业大学 | A kind of discrimination method of strange nanmu agalloch eaglewood and the common agalloch eaglewood of Huian system |
| WO2019209099A1 (en) * | 2018-04-23 | 2019-10-31 | Universiti Malaysia Pahang (Ump) | A method of determining grade of agarwood oil at ambient temperature |
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