JP2009008664A - Ingredient analysis method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ingredient analysis method which can perform a quantitative analysis as well as a qualitative analysis of ingredients contained in cosmetics. <P>SOLUTION: The ingredient analysis method for analyzing at least one ingredient contained in a mixture having a plurality of ingredients, includes the steps of: heating the mixture and measuring its weight change; and analyzing gas generated from the heated mixture. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a component analysis method for analyzing at least one component contained in a mixture containing a plurality of components.

  Conventionally, when analyzing ingredients contained in cosmetics such as powdery foundations, organic solvents are separated by extracting solubles such as oils and surfactants from cosmetics using a solvent. In this method, a constituent component is further extracted from the organic powder using the above solvent, and the insoluble matter is ignited. However, in addition to the time required for extraction, there is a problem that the quantitativeness and qualitative properties are insufficient.

On the other hand, as a thermal analyzer, a thermogravimetric measuring device (TG), a differential thermogravimetric simultaneous measuring device (TG-DTA) and the like are known. In addition, there is also known an apparatus in which a mass spectrometer (MS) or an infrared spectrophotometer (IR) is attached to a thermal analyzer, and gas generated from a sample heated by the thermal analyzer is introduced into the MS or IR for analysis. (See Patent Documents 1 and 2). Non-Patent Document 1 discloses TG-DTA / GC-MS as an analysis method for thermal decomposition.
Japanese Patent Laid-Open No. 5-60709 JP-A-6-265492 Arai Tadashi, Senda Tetsuya, Rigaku Denki Journal, 25 (1), 1994, 41

  The present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to provide a component analysis method capable of performing qualitative analysis and quantitative analysis of components contained in cosmetics.

  The invention according to claim 1 is a component analysis method for analyzing at least one component contained in a mixture containing a plurality of components, wherein the mixture is heated to measure a change in weight of the mixture with respect to temperature. And a step of analyzing a gas generated from the heated mixture.

  The invention according to claim 2 is the component analysis method according to claim 1, wherein the gas generated from the heated mixture is gas chromatograph-mass spectrometer (GC-MS) and / or infrared spectrophotometer ( (IR).

  The invention according to claim 3 is the component analysis method according to claim 1 or 2, wherein the mixture is a cosmetic.

  The invention according to claim 4 is the component analysis method according to claim 1 or 2, further comprising the step of obtaining the mixture by extraction with one or more solvents.

  The invention according to claim 5 is the component analysis method according to claim 4, wherein the mixture is obtained by extracting cosmetics with the one or more solvents.

  ADVANTAGE OF THE INVENTION According to this invention, while performing the qualitative analysis of the component contained in cosmetics, the component analysis method which can carry out a quantitative analysis can be provided.

  Next, the best mode for carrying out the present invention will be described with reference to the drawings.

  The component analysis method of the present invention comprises a step of analyzing at least one component contained in a mixture containing a plurality of components, heating the mixture, and measuring a change in weight of the mixture with respect to temperature, and generating from the heated mixture Analyzing the generated gas. At this time, the means for heating the mixture and measuring the change in the weight of the mixture with respect to temperature is not particularly limited, but a known thermogravimetric measurement device (TG), differential thermogravimetric simultaneous measurement device (TG-DTA), etc. Can be used. The means for analyzing the gas generated from the heated mixture is not particularly limited, and a known gas chromatograph-mass spectrometer (GC-MS), infrared spectrophotometer (IR), etc. can be used. Two or more kinds may be used in combination.

  FIG. 1 shows a TG / GC-MS as an example of a component analyzer used in the present invention. The component analyzer 10 includes a TG 11 that heats the mixture and measures a change in the weight of the mixture with respect to temperature, and a GC-MS 12 that analyzes a gas generated from the mixture heated by the TG 11. In addition, although it does not specifically limit as MS, It is preferable to use a quadrupole mass spectrometer (Q-MS). At this time, the gas generated from the mixture heated by the TG 11 is sent to the GC-MS 12 via the transfer line 13 whose temperature is adjusted to 200 to 300 ° C. by the carrier gas. The operation of the TG 11 is controlled by the computer 14, and the operation of the GC-MS 12 is controlled by the computer 15. Moreover, a well-known apparatus can be used as TG11 and GC-MS12. Furthermore, when analyzing the MS spectrum obtained by GC-MS12, it is preferable to use a database of MS spectra measured in advance. When component analysis is performed using such a component analysis apparatus 10, quantitative analysis can be performed with the TG 11 and qualitative analysis can be performed with the GC-MS 12.

  FIG. 2 shows TG / IR as another example of the component analyzer used in the present invention. The component analyzer 20 includes a TG 21 that heats the mixture and measures a change in weight with respect to temperature, and an IR 22 that analyzes a gas generated from the mixture heated by the TG 21. As IR22, it is preferable to use a Fourier transform infrared spectrophotometer (FT-IR). At this time, the gas generated from the mixture heated by the TG 21 is sent to the IR 22 through the transfer line 23 whose temperature is adjusted to 200 to 300 ° C. by the carrier gas. The operation of the TG 21 is controlled by the computer 23, and the operation of the IR 22 is controlled by the computer 24. In TG21, the temperature may be changed at a constant rate, but it is preferable to reduce the temperature change when the weight change of the mixture is large and to increase the temperature change when the weight change is small. Thereby, the separation resolution can be improved and the analysis time can be shortened. In addition, a well-known apparatus can be used as TG21 and IR22. Moreover, when analyzing the IR spectrum obtained by IR22, it is preferable to use a database of IR spectra measured in advance. When component analysis is performed using such a component analyzer 20, quantitative analysis can be performed with the TG 21 and qualitative analysis can be performed with the IR 22. In addition, when the weight change of the some component contained in a mixture cannot be quantified with TG21, you may quantify with IR22.

  In the present invention, TG / GC-MS and TG / IR may be used in combination.

  Examples of the mixture analyzed using the component analysis method of the present invention include cosmetics such as powdery foundation containing organic powder. In addition, when analyzing cosmetics using the component analysis method of the present invention, the cosmetics may be analyzed directly, or may be analyzed after extracting the cosmetics using a solvent such as hexane or methanol. Good.

  Using TG / GC-MS (see FIG. 1), component analysis was performed on a two-component mixture in which the weight ratio of nylon powder to PMMA powder was 1. Note that TG-8120 (manufactured by Rigaku Corporation) was used as TG11, and 5973MS (manufactured by Agilent Technologies) was used as GC-MS12, and the temperature of transfer line 13 was adjusted to 270 ° C.

  FIG. 3 shows a TG curve obtained by heating the mixture at a heating rate of 10 ° C./min using TG / GC-MS. 4 shows gas chromatograms of gas generated from the mixture heated to 1000 ° C., and FIGS. 5 (a) and 5 (b) show the peak A (retention time: 34.573 minutes) and peak of FIG. The MS spectrum in B (retention time: 43.069 minutes) is shown. FIGS. 6A and 6B show MS spectra of PMMA and nylon retrieved from the database, respectively. Since the MS spectra in FIGS. 5 (a) and 6 (a) and FIGS. 5 (b) and 6 (b) are similar, peak A and peak B in FIG. 4 are peaks of PMMA and nylon, respectively. It was estimated.

  Next, component analysis was performed on the PMMA powder and the nylon powder using TG / GC-MS in the same manner as described above. 7A and 7B show TG curves of PMMA powder and nylon powder, respectively. FIG. 7 shows that PMMA powder and nylon powder decompose 100%.

  FIGS. 8A and 8B show gas chromatograms of gases generated from PMMA powder and nylon powder heated to 1000 ° C., respectively, and FIGS. 9A and 9B show the peaks of FIG. The MS spectrum in A '(retention time: 33.809 minutes) and peak B' (retention time: 43.150 minutes) is shown. At this time, the MS spectra of FIGS. 5 (a) and 9 (a) and FIGS. 5 (b) and 9 (b), the peak A of FIG. 4 and the peak A ′ of FIG. 8, and the peak B of FIG. Since peak 8 ′ of 8 is similar, peak A and peak B were identified as peaks of PMMA powder and nylon powder, respectively.

FIG. 10 shows a TG curve (see FIGS. 3 and 7) and a DTG curve of the mixture, PMMA powder and nylon powder. From FIG. 10, the weight change of the mixture and the PMMA powder from the start of the decomposition of the PMMA powder to the inflection point P in the region where the weights of the two components of the TG curve of the mixture both decrease is −50.28 % And −94.82%. Moreover, it turns out that the weight change of the mixture and nylon powder from the inflection point P to the completion | finish of decomposition | disassembly of nylon powder is -42.12% and -80.91%, respectively. From this, calculating the weight ratio of nylon powder to PMMA powder,
42.12 / 80.91 / (50.28 / 94.82) = 0.98
It becomes.

  Therefore, it can be seen that a two-component mixture in which the decomposition temperatures partially overlap can be quantified with sufficient accuracy.

  In the same manner as in Example 1, a TG / GC-MS was used for component analysis of a two-component mixture of silicone powder having a polymethylsilsesquioxane weight ratio of 1 to (dimethicone / vinylmethicone) crosspolymer. .

  FIG. 11 shows a TG curve obtained by heating the mixture at a heating rate of 10 ° C./min using TG / GC-MS. FIG. 12 shows gas chromatograms of gas generated from a mixture heated to 1000 ° C., and FIGS. 13A and 13B show MS spectra at peak A and peak B in FIG. 12, respectively.

  Next, the component analysis of (dimethicone / vinylmethicone) crosspolymer and polymethylsilsesquioxane was performed using TG / GC-MS in the same manner as described above. FIGS. 14A and 14B show TG curves of (dimethicone / vinylmethicone) crosspolymer and polymethylsilsesquioxane, respectively. FIG. 14 shows that (dimethicone / vinylmethicone) crosspolymer decomposes 99.57%, while polymethylsilsesquioxane decomposes 8.55%.

  FIGS. 15A and 15B show gas chromatograms of gases generated from (dimethicone / vinyl methicone) crosspolymer and polymethylsilsesquioxane heated to 1000 ° C., respectively. (B) shows the MS spectra at peak A ′ and peak B ′ in FIG. 15, respectively. At this time, the MS spectra of FIGS. 13 (a) and 16 (a) and FIGS. 13 (b) and 16 (b), the peak A of FIG. 12 and the peak A ′ of FIG. 15, and the peak B of FIG. Since 15 peaks B ′ are similar, peak A and peak B were identified as (dimethicone / vinylmethicone) crosspolymer and polymethylsilsesquioxane peaks, respectively.

FIG. 17 shows a TG curve (see FIGS. 11 and 14) of the mixture, (dimethicone / vinyl methicone) crosspolymer and polymethylsilsesquioxane. From FIG. 17, the weight change of the mixture and the (dimethicone / vinyl methicone) cross polymer from the start of the decomposition of the (dimethicone / vinyl methicone) cross polymer to the end of the decomposition was −50.34% and − It turns out that it is 99.57%. The weight changes of the mixture and polymethylsilsesquioxane from the start of the decomposition of polymethylsilsesquioxane to the end of the decomposition are −3.77% and −8.55%, respectively. I understand that. From this, calculating the weight ratio of polymethylsilsesquioxane to (dimethicone / vinylmethicone) crosspolymer,
3.77 / 8.55 / (50.34 / 99.57) = 0.87
It becomes.

  Therefore, it can be seen that a two-component mixture of silicone powders whose decomposition temperatures do not overlap can be quantified with sufficient accuracy. Note that such a two-component mixture of silicone powders cannot be separated by extraction.

  Polymethylsilsesquioxane 1.0% by weight, (dimethicone / vinyl dimethicone) crosspolymer 4.0% by weight, silicone-treated mica titanium 3.5% by weight, fatty acid metal-treated titanium dioxide 8.0% by weight, silicone-treated oxidation Iron 0.3 wt%, purified water residue, octyl methoxycinnamate 1.0 wt%, disteardimonium hectorite 1.0 wt%, dimethicone 3.0 wt%, decamethylcyclopentasiloxane 32.0 wt% , 3.0% by weight of polyoxyethylene-modified dimethylpolysiloxane, 8.0% by weight of glycerin, 4.0% by weight of dipropylene glycol, 0.4% by weight of palmitic acid, 0.2% by weight of distearyldimonium chloride, methylparaben 0.2% by weight, phenoxyethanol 0.3% by weight, EDTA 0.1% by weight and perfume The composed foundation was extracted with hexane and ethanol, insoluble matter was 18.0 wt%.

Next, when insoluble components were analyzed using TG / GC-MS in the same manner as in Example 2, it was found that (dimethicone / vinyl methicone) crosspolymer and polymethylsilsesquioxane were contained in the insoluble components. all right. FIG. 18 shows a TG curve obtained by heating an insoluble component, (dimethicone / vinylmethicone) crosspolymer and polymethylsilsesquioxane at a heating rate of 10 ° C./min using TG / GC-MS. . From FIG. 18, the insoluble matter and the change in weight of the (dimethicone / vinyl methicone) cross polymer from the start of the decomposition of the (dimethicone / vinyl methicone) cross polymer to the end of the decomposition were −23.70% It turns out that it is -99.31%. The weight changes of the mixture and the polymethylsilsesquioxane from the start of the decomposition of the polymethylsilsesquioxane to the end of the decomposition are -0.62% and -8.42%, respectively. I understand that. From this, when calculating the blending amount of (dimethicone / vinyl methicone) cross polymer in the foundation,
18.0 × 23.7 / 99.31 = 4.3 [wt%]
It becomes. Furthermore, when calculating the amount of polymethylsilsesquioxane in the foundation,
18.0 × 0.62 / 8.42 = 1.3 [wt%]
It becomes.

  Therefore, it turns out that the compounding quantity of two components of the silicone powder with which the decomposition temperature contained in a foundation does not overlap can be quantified with sufficient precision.

  Using TG / IR (see FIG. 2), a ternary mixture of polymethylsilsesquioxane, (dimethicone / vinylmethicone / methicone) and (dimethicone / vinylmethicone) crosspolymer (weight ratio = 3) : 2: 1) was subjected to component analysis. Note that TG-8120 (manufactured by Rigaku Corporation) was used as TG21, and MagnaIR-550 (manufactured by Thermo Fisher Scientific Co., Ltd.) was used as IR22, and the temperature of transfer line 23 was adjusted to 230 ° C.

  FIG. 19 shows a TG curve obtained by heating the mixture at a temperature rising rate of 20 ° C./min using TG / IR. FIGS. 20A and 20B show IR spectra of gases generated after 22 minutes and 40 minutes, respectively. From the IR spectrum retrieved from FIG. 20 and the database, it was found that the mixture contained polymethylsilsesquioxane, (dimethicone / vinylmethicone / methicone) crosspolymer and (dimethicone / vinylmethicone) crosspolymer. For this reason, FIG. 19 also shows TG curves obtained by heating polymethylsilsesquioxane, (dimethicone / vinylmethicone / methicone) crosspolymer, and (dimethicone / vinylmethicone) crosspolymer under the same conditions. . At this time, the mixture may be qualitatively analyzed using TG / GC-MS in the same manner as in Example 2.

  From FIG. 19, the weight changes of the mixture and polymethylsilsesquioxane from the start of the decomposition of polymethylsilsesquioxane to the end of the decomposition are −3.7% and −6.0%, respectively. It can be seen that it is. Further, from FIG. 19, a mixture from the start of the decomposition of (dimethicone / vinyl methicone / methicone) cross polymer and (dimethicone / vinyl methicone) cross polymer to the end of the decomposition, (dimethicone / vinyl methicone / methicone) It can be seen that the weight changes of the crosspolymer and (dimethicone / vinylmethicone) crosspolymer are -46.0%, -70.0% and -100.0%, respectively.

FIG. 21 shows a mixture of (dimethicone / vinyl methicone / methicone) crosspolymer and (dimethicone / vinyl methicone) crosspolymer (weight ratio = 1: 1, 2: 1, 3: 1) using TG / IR. An IR spectrum of a gas generated after 22 minutes of heating at a temperature rate of 20 ° C./min is shown. FIG. 21 shows that the mixtures having different weight ratios have different IR spectrum peaks at 3016 cm ⁻¹ and 2970 cm ⁻¹ .

FIG. 22 shows a calibration curve obtained using the ratio of the height of the peak at 3016 cm ^{−1 to} the peak at 2970 cm ^{−1 in} the IR spectrum of FIG.

Next, using TG / IR, the mixture was heated at a heating rate of 20 ° C./min, and the IR spectrum of the gas generated after 22 minutes (see FIGS. 20A and 23) with respect to the peak at 2970 cm ⁻¹ . The peak height ratio at 3016 cm ⁻¹ was determined to be 0.873. From this, the weight ratio of (dimethicone / vinyl methicone / methicone) cross polymer to (dimethicone / vinyl methicone) cross polymer is
(0.873 + 0.0812) /0.545=1.75
It becomes.

Furthermore, the weight ratio of polymethylsilsesquioxane to (dimethicone / vinyl methicone) crosspolymer is:
(3.7 / 6.0) / {46 / (70 × 1.75 + 100) = 2.98
It becomes.

  Therefore, it can be seen that a three-component mixture of silicone powders having a different decomposition temperature and a substantially identical one can be quantified with sufficient accuracy. In addition, since the decomposition temperature of such (dimethicone / vinyl methicone / methicone) crosspolymer and (dimethicone / vinyl methicone) crosspolymer is almost the same, such a ternary mixture of silicone powders is TG / GC-MS. Cannot be quantified. In addition, such a three-component mixture of silicone powder cannot be separated by extraction.

It is a block diagram which shows an example of the component analyzer of this invention. It is a block diagram which shows the other example of the component analyzer of this invention. 2 is a diagram showing a TG curve of the mixture of Example 1. FIG. 3 is a diagram showing a gas chromatogram of gas generated from the mixture of Example 1. FIG. It is a figure which shows the MS spectrum in the peak A and peak B of FIG. It is a figure which shows the MS spectrum of PMMA and nylon searched from the database. It is a figure which shows the TG curve of PMMA powder and nylon powder. It is a figure which shows the gas chromatogram of the gas emitted from PMMA powder and nylon powder. It is a figure which shows the MS spectrum in the peak A 'and peak B' of FIG. It is a figure which shows the TG curve and DTG curve of the mixture of Example 1, PMMA powder, and nylon powder. 2 is a diagram showing a TG curve of the mixture of Example 2. FIG. 3 is a diagram showing a gas chromatogram of gas generated from the mixture of Example 2. FIG. It is a figure which shows the MS spectrum in the peak A and peak B of FIG. It is a figure which shows the TG curve of a (dimethicone / vinyl methicone) crosspolymer and polymethylsilsesquioxane. It is a figure which shows the gas chromatogram of the gas emitted from the (dimethicone / vinyl methicone) crosspolymer and polymethylsilsesquioxane. It is a figure which shows the MS spectrum in the peak A 'and peak B' of FIG. It is a figure which shows the TG curve of the mixture of Example 2, (dimethicone / vinyl methicone) crosspolymer, and polymethylsilsesquioxane. It is a figure which shows the TG curve of the insoluble part of Example 3, (dimethicone / vinyl methicone) crosspolymer, and polymethylsilsesquioxane. It is a figure which shows the TG curve of the mixture of Example 4, polymethylsilsesquioxane, (dimethicone / vinyl methicone / methicone) crosspolymer, and (dimethicone / vinyl methicone) crosspolymer. It is a figure which shows the IR spectrum of the gas which heated the mixture of Example 4 by the temperature increase rate of 20 degree-C / min, and was generated after 22 minutes and 40 minutes. A mixture of (dimethicone / vinylmethicone / methicone) crosspolymer and (dimethicone / vinylmethicone) crosspolymer (weight ratio = 1: 1, 2: 1, 3: 1) was heated at a heating rate of 20 ° C./min to be 22 It is a figure which shows IR spectrum of the gas generated after minutes. Is a diagram showing a calibration curve obtained by using the ratio of the height of the peak of 3016cm ^-1 to the peak of the IR spectrum of 2970cm ^-1 in Figure 21. It is an enlarged view of IR spectrum of the gas generated after heating the mixture of Example 4 at a heating rate of 20 ° C./min and 22 minutes later.

Explanation of symbols

10, 20 Component analyzer 11, 21 TG
12 GC-MS
13 Transfer line 14, 15, 23, 24 Computer 22 IR

Claims (5)

A component analysis method for analyzing at least one component contained in a mixture containing a plurality of components,
Heating the mixture to measure a change in weight of the mixture with respect to temperature;
A component analysis method comprising a step of analyzing a gas generated from the heated mixture.   The component analysis according to claim 1, wherein the gas generated from the heated mixture is analyzed using a gas chromatograph-mass spectrometer (GC-MS) and / or an infrared spectrophotometer (IR). Method.   The component analysis method according to claim 1, wherein the mixture is a cosmetic.   The component analysis method according to claim 1, further comprising a step of obtaining the mixture by extraction with one or more solvents.   The component analysis method according to claim 4, wherein the mixture is obtained by extracting cosmetics with the one or more solvents.

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