KR102019139B1 - A method analyzing trace material of fragrance composition - Google Patents

Abstract

The present invention relates to a trace material analysis method of the fragrance composition through gas chromatographic vacuum ultraviolet (GC-VUV) analysis, and more particularly, a trace material not found by GC-MS by analyzing the fragrance composition through GC-VUV analysis And a method for detecting a hazardous substance.

Description

{A method analyzing trace material of fragrance composition}

The present invention relates to a trace material analysis method of the perfume composition through gas chromatography-vacuum ultraviolet (GC-VUV) analysis. A method for detecting substances and harmful substances.

In recent years, harmful substances have been found among many of the products we use, which has become a social problem. In particular, according to the survey by the Consumer Protection Agency, HICC (Prohibition on Use of European Union (EU) as a safety issue in perfumes imported into Korea, Limonene components that could cause side effects such as hydroxyisohexyl-3-cyclohexenecarbox aldehyde) components and contact dermatitis were detected.

Limonene, a harmful trace substance, is a fragrance chemical as a constituent of perfume, and HICC has been known to cause fragrance allergy most frequently since the publication of the 1999 report by the SCCNFP.

Therefore, consumers are concerned about the presence of traces of harmful substances in the fragrance sprayed on the skin and environmentally friendly fragrances used in processed foods for human consumption. Companies are focusing on securing technologies to analyze these traces of harmful substances. . Detection of such traces of harmful substances is carried out through various methods, a typical method is GS-MS.

In this regard, Korean Patent Laid-Open Publication No. 2006-0132600 discloses a method for analyzing organic chemical substances including environmental hormones and perfumes by liquid chromatography and gas chromatography.

In addition, Korean Patent Publication No. 2007-0040374 discloses a method for identifying or evaluating compounds useful in the field of perfumes and fragrances.

However, the GS-MS analysis technique disclosed in the above-mentioned literature does not have good sensitivity when the peaks of trace materials overlap, and it is difficult to detect such isomers, so it is not effective for detecting trace harmful substances of perfume.

Korean Laid-Open Patent No. 2006-0132600 Korean Patent Publication No. 2007-0040374

An object of the present invention is to provide a method for analyzing the trace amount of harmful substances contained in the fragrance composition through GC-VUV analysis.

In addition, an object of the present invention is to provide a method for effectively analyzing a trace substance at a high speed through GC-VUV analysis compared to the conventional analysis method GC-MS.

In order to achieve the above object, the present invention comprises the steps of sampling the fragrance composition; Supplying the sampled fragrance composition to GC-VUV; Applying heat to the supplied perfume composition; Injecting the heated flavor composition into a column; Irradiating ultraviolet rays to the fragrance composition passing through the column to excite; And it provides a trace material analysis method of the fragrance composition comprising the step of analyzing the excited fragrance composition.

In one embodiment of the present invention, the step of applying the heat is characterized in that to increase the temperature at a temperature increase rate of 10 ~ 25 ℃ / min from 50 ℃ to 320 ℃.

In one embodiment of the present invention, the trace substance is characterized in that the harmful substance.

In one embodiment of the present invention, the trace material is 2-ethylhexylacetate, 2-methyl-4-n-propylbenzene, 1-methyl-4-n-propylbenzene, 1-methyl- It is characterized in that at least one of 4-ethylbenzene (1-Methyl-4-ethylbenzene) and butyric acid methyl ester (butyric acid methyl ester).

The present invention can provide a method for analyzing the trace amount of harmful substances included in the perfume composition through GC-VUV analysis.

In addition, the present invention can provide a method for rapidly and effectively analyzing a trace material that is not detected in the existing analysis method GC-MS through GC-VUV analysis.

In addition, the present invention by optimizing the sampling conditions and heat treatment conditions, 2-ethylhexylacetate (2-ethylhexylacetate), 1-methyl-4-n-propylbenzene (1-methyl-4-n) at a faster rate than conventional GS-MS Eco-friendly fragrance composition that does not contain harmful substances because it can effectively detect traces such as -propylbenzene), 1-methyl-4-ethylbenzene, and butyric acid methyl ester Can be provided.

1 shows the structure of the GC-VUV of the present invention.
Figure 2 shows the results of GC-MS and GC-VUV analysis of the natural tea fragrance of the present invention: (a) GC-MS, (b) GC-VUV.
Figure 3 shows the results of GC-MS and GC-VUV analysis of the natural rosemary flavor of the present invention: (a) GC-MS, (b) GC-VUV.
Figure 4 shows the results of GC-MS and GC-VUV analysis of the synthetic strawberry flavor of the present invention: (a) GC-MS, (b) GC-VUV.

Hereinafter, the present invention will be described in detail with reference to Examples. The terms, examples, etc. used in the present invention are merely illustrated to explain the present invention in more detail and to help those skilled in the art, and the scope of the present invention is not limited thereto.

Technical terms and scientific terms used in the present invention represent the meanings that are commonly understood by those of ordinary skill in the art unless otherwise defined.

The present invention relates to a trace material analysis method of the fragrance composition through GC-VUV (Gas Chromatography Vacuum Ultraviolet).

In order to achieve the above object, the present invention comprises the steps of sampling the fragrance composition; Supplying the sampled fragrance composition to GC-VUV; Applying heat to the supplied perfume composition; Injecting the heated flavor composition into a column; Irradiating ultraviolet rays to the fragrance composition passing through the column to excite; And analyzing the excited fragrance composition.

GC-VUV analyzes the fragrance composition through the structure as shown in FIG.

Samples are sampled and injected into the GC-VUV, heated to vaporize the sample, and then injected into a GC column. The sample passed through the column passes through the flow cell through the transfer line of the VUV detector.

At this time, the sample passing through the flow cell is excited by absorbing the VUV wavelength emitted from the lamp. Through this process, the absorption wavelength is detected by the detector.

The detector will have an absorption spectrum equivalent to synchrotron and can be intuitively verified through software. After that, it is analyzed qualitatively through library on software and can be quantitatively analyzed using Absorption cross section of each component.

VUV (Vacuum Ultraviolet) is a kind of electromagnetic radiation and refers to the short wavelength of 240nm or less in the ultraviolet region (10 ~ 400nm), and the gas phase compound strongly absorbs the wavelength in the 115 ~ 185nm region, the VUV wavelength. Therefore, it can be used for analysis of the compound.

GC-VUV can distinguish isomers that are difficult to distinguish from GC-MS, and have the advantage of distinguishing wavelengths even when peaks overlap.

In GC-VUV, reactions in the σ → σ * (very high energy, far ultraviolet range with 100 ~ 180nm vacuum UV region) and π → π * (UV / VIS) are not found in traditional UV / VIS absorption spectroscopy. It is not always found in the region, and the reaction of the region (125-240 nm) can be confirmed, and it is possible to distinguish between isomers and trace substances.

Applicants conducted experiments by varying the sampling conditions and heat treatment conditions in order to analyze various trace substances included in the perfume composition, and confirmed that the analysis peak of the perfume composition changes according to the heat treatment conditions, used in this experiment In the case of modified perfume compositions, 2-ethylhexylacetate, 1-methyl-4-n-propylbenzene, which is not detected in conventional GS-MS analysis under certain heat treatment conditions ), Harmful traces such as 1-methyl-4-ethylbenzene and butyric acid methyl ester at high speed (less than 30 minutes, preferably less than 15 minutes) It was confirmed that it can be detected effectively.

The step of applying the heat is applied to the supplied perfume composition, wherein the supplied perfume composition is heat-treated by applying heat at a temperature increase rate of 10-25 ℃ / min from 50 ℃ to 320 ℃.

In particular, the step of applying heat to the fragrance composition is maintained for 1 to 10 minutes at 50 ℃, heat is applied at a temperature rising rate of 10 to 25 ℃ / min from 50 ℃ to 250 ℃, then 1 to 10 minutes at 250 ℃ After holding, heat is applied at a temperature increase rate of 10 to 25 ° C./min from 250 ° C. to 320 ° C., and then maintained at 320 ° C. for 1 to 10 minutes.

In addition, the step of applying heat to the fragrance composition is maintained for 1 to 10 minutes at 50 ℃, heat is applied at a temperature rising rate of 10 to 25 ℃ / min from 50 ℃ to 150 ℃, then maintained at 150 ℃ 1 to 10 minutes Then, heat was applied at a temperature increase rate of 10-25 ° C./min from 150 ° C. to 250 ° C., and then maintained at 250 ° C. for 1 to 10 minutes, and then a temperature increase rate of 10-25 ° C./min from 250 ° C. to 320 ° C. After the furnace is heated, it is preferably maintained at 320 ° C. for 1 to 10 minutes.

By performing the heat treatment conditions as described above it is possible to effectively detect the reaction excited by the ultraviolet irradiation, it is possible to accurately analyze the trace amount of harmful substances contained in the perfume composition.

In the analysis of natural tea fragrance, benzene was detected as a harmful substance by GC-MS, but much less harmful 1-methyl-4-n-propylbenzene was detected by GC-VUV. In addition, methyl cis-9,10 was detected. By detecting -methylenehexadecanoate, trace substances can be detected more accurately.

In the analysis of natural rosemary fragrances, GC-MS detected 1-methyl-4-ethylbenzene, a harmful substance that was not detected. In addition, methyl cis-9,10-methylenehexadecanoate, etc., can detect trace substances more accurately. have.

In the analysis of synthetic strawberry flavors, butyric acid methyl ester and 2-ethylhexyl acetate, which were not detected by GC-MS, were detected.

The advantage of GC-VUV that can detect such a trace amount of harmful components is the detection rate, the present invention can control the analysis time by adjusting the temperature increase rate during the heat treatment of the perfume composition.

When raising the fragrance composition of the present invention at a rate of 10 ℃ / min, 15 ℃ / min, 20 ℃ / min from 50 ℃ to 320 ℃ all traces of harmful substances were detected, when the temperature increase rate, sampling time Because of this reduction, it is possible to quickly detect trace harmful substances in the field and use them in the development of eco-friendly fragrances.

    The present invention will be described in detail through the following examples. The following examples are merely illustrative for the practice of the present invention, but the content of the present invention is not limited by the following examples.

    (GC-MS) (Instrument: Agilent 7890B-GC / 5977a-MS)

Injection: 1 μl

Inlet heater: 280 ℃

Split ratio: 10 to 1

Column: HP-5ms (30m * 250㎛, film: 0.25㎛) agilent

Flow rate: Helium, 1ml / min

Oven: 40 degreeC (5min) hold | maintain, 5 degreeC / min, temperature rise to 120 degreeC, 20 degreeC / min, temperature rise to 300 degreeC

Aux heater: 280 ℃

Solvent delay: 2.0min

Scan: 10-600m / z

(GC-VUV) (Instrument: VUV-ANALYTICS VGA-100)

Inlet: 320 ℃, split: 20 to 1

Injection volume: lµl

Column: RXI-1MS 30M 0.25MMID 0.5UM

Oven: Hold at 50 ° C for 2 minutes, heat up to 250 ° C at a rate of 10 ° C / min, hold at 250 ° C for 5 minutes, raise to 320 ° C at 10 ° C / min, and hold at 320 ° C for 5 minutes

Makeup gas: N ₂

Column flow: 2ml / min

Split ratio: 30 to 1

(Example 1)

Tea tree E.O (New diractions, Australia) was used as a natural tea flavor.

After adding 1 μl of natural tea fragrance, the results of analysis using GC-MS and GC-VUV are shown in FIG. 2.

In GC-VUV, the supplied perfume composition was heated and excited by irradiation with ultraviolet rays, and then the excited perfume composition was analyzed.

At this time, the heat treatment is maintained for 2 minutes at 50 ℃, the heat is applied at a rate of 10 ℃ / min from 50 ℃ to 250 ℃, then maintained for 5 minutes at 250 ℃, 10 ℃ from 250 ℃ to 320 ℃ Heat was applied at a rate of / min and then held at 320 ° C. for 5 minutes.

As can be seen in Figure 2, when using the GC-VUV, the analysis is completed within 30 minutes, the hazardous material can be seen that the analysis is completed within 15 minutes.

Table 1 shows the traces analyzed using GC-MS and GC-VUV.

GC-MS GC-VUV Hexane Alpha-pine 1R-Alpha-Pinene 1-methyl-4-n-propylbenzene Alpha terpinene Gamma-terpinene Methyl cis-9,10-methylene
hexadecanoate Benzene Palmitic acid methyl ester Gamma-terpinene

As a result of analyzing natural tea fragrance, benzene was detected as harmful substance by GC-MS, but much less harmful substance 1-methyl-4-n-propylbenzene was detected by GC-VUV, and methyl cis-9,10 By detecting -methylenehexadecanoate, trace substances can be detected more accurately.

(Example 2)

Rosemary E.O (Florida Chemical, USA) was used as a natural rosemary fragrance.

After adding 1 μl of natural rosemary flavor, the result of analysis by GC-MS and GC-VUV is shown in FIG. 3.

In GC-VUV, the supplied perfume composition was heated and excited by irradiation with ultraviolet rays, and then the excited perfume composition was analyzed.

At this time, the heat treatment is maintained for 2 minutes at 50 ℃, the heat is applied at a rate of 10 ℃ / min from 50 ℃ to 250 ℃, then maintained for 5 minutes at 250 ℃, 10 ℃ from 250 ℃ to 320 ℃ Heat was applied at a rate of / min and then held at 320 ° C. for 5 minutes.

As can be seen in Figure 3, when using the GC-VUV, the analysis is completed within 30 minutes, the hazardous material can be seen that the analysis is completed within 15 minutes.

Table 2 shows the traces analyzed using GC-MS and GC-VUV.

GC-MS GC-VUV Gamma-terpinene Alpha-pine Camphene Beta-Pinene Bicyclo [3,1,1] heptane 1-methyl-4-ethylbenzene 1,8-Cineole 1,8-Cineole Camphor Camphor Bornyl acetate Methyl cis-9,10-methylene
hexadecanoate trans-Caryophyllene Palmitic acid methyl ester

Natural rosemary fragrance was analyzed by GC-VUV. As a result, GC-MS detected 1-methyl-4-ethylbenzene, a harmful substance that was not detected, and methyl cis-9,10-methylenehexadecanoate. Can be detected accurately.

(Example 3)

Ethyl butyrate 30%, Iso-amyl acetate 5%, cis-3-hexanol 15%, Linalool 10%, Ethyl Maltol 25%, r-decalacetone 5%, butyric acid 10% to prepare a synthetic strawberry flavor.

4 μl of natural synthetic strawberry flavor was added and analyzed by GC-MS and GC-VUV.

In GC-VUV, the supplied perfume composition was heated and excited by irradiation with ultraviolet rays, and then the excited perfume composition was analyzed.

At this time, the heat treatment is maintained for 2 minutes at 50 ℃, the heat is applied at a rate of 10 ℃ / min from 50 ℃ to 250 ℃, then maintained for 5 minutes at 250 ℃, 10 ℃ from 250 ℃ to 320 ℃ Heat was applied at a rate of / min and then held at 320 ° C. for 5 minutes.

As can be seen in Figure 4, when using the GC-VUV, it can be seen that the analysis is completed within 15 minutes.

Table 3 shows the traces analyzed using GC-MS and GC-VUV.

GC-MS GC-VUV Hexane Butyric acid methyl ester Hexanedioic acid 2- Ethylhexyl  acetate Hexanoic acid Linalool

As a result of analyzing synthetic strawberry fragrance by GC-VUV, butyric acid methyl ester and 2-ethylhexyl acetate, which were not detected by GC-MS, were detected. have.

(Example 4)

In GC-VUV analysis, the same method as in Examples 1 to 3 except that the temperature increase rate from 50 ° C to 250 ° C was adjusted to 5 ° C / min, 15 ° C / min, 20 ° C / min, 30 ° C / min. The fragrance composition was analyzed by GC-VUV.

       1-Methyl-4-n-propylbenzene, 1-Methyl-4-ethylbenzene, Butyric acid methyl ester and 2-Ethylhexyl acetate were analyzed and detected.

Temperature rise rate Natural Tea Tree Spice Natural Rosemary Spice Synthetic strawberry spices 1-Methyl-4-n-
propylbenzene 1-Methyl-4-ethylbenzene Butyric acid methyl ester 2-Ethylhexyl acetate 5 ℃ / min × ○ × × 15 ℃ / min ○ ○ ○ ○ 20 ℃ / min ○ ○ ○ ○ 30 ℃ / min × × × ○

When the rate of temperature increase from 50 ° C. to 250 ° C. is adjusted to 15 ° C./min and 20 ° C./min, all four trace substances are detected, and the temperature increase rate is adjusted to 5 ° C./min and 30 ° C./min. Some traces were not detected.

(Example 5)

In the GC-VUV analysis, through the GC-VUV in the same manner as in Examples 1 to 3, except that heat was applied at a rate of 10 ° C / min from 50 ° C to 320 ° C without the step of holding at 250 ° C for 5 minutes. Perfume composition was analyzed.

       1-Methyl-4-n-propylbenzene, 1-Methyl-4-ethylbenzene, Butyric acid methyl ester and 2-Ethylhexyl acetate were analyzed and detected.

Natural Tea Tree Spice Natural Rosemary Spice Synthetic strawberry spices 1-Methyl-4-n-
propylbenzene 1-Methyl-4-ethylbenzene Butyric acid methyl ester 2-Ethylhexyl acetate ○ × × ○

Some traces were not detected when the rate of temperature increase from 50 ° C. to 320 ° C. was adjusted to 10 ° C./min without the step of holding at 250 ° C. for 5 minutes.

(Example 6)

In GC-VUV analysis, after holding at 50 ° C. for 2 minutes, heat was applied at a temperature rising rate of 10 ° C./min from 50 ° C. to 150 ° C., and then maintained at 150 ° C. for 5 minutes, and then at 150 ° C. to 250 ° C. Heat was applied at a rate of temperature increase of ℃ / min, and then maintained at 250 ℃ for 5 minutes, then heat was applied at a temperature increase rate of 10 ℃ / min from 250 ℃ to 320 ℃, and then maintained at 320 ℃ 5 minutes Was analyzed fragrance composition through GC-VUV in the same manner as in Examples 1-3.

       1-Methyl-4-n-propylbenzene, 1-Methyl-4-ethylbenzene, Butyric acid methyl ester and 2-Ethylhexyl acetate were analyzed and detected.

Natural Tea Tree Spice Natural Rosemary Spice Synthetic strawberry spices 1-Methyl-4-n-
propylbenzene 1-Methyl-4-ethylbenzene Butyric acid methyl ester 2-Ethylhexyl acetate ○ ○ ○ ○

When the rate of temperature increase was adjusted to the above conditions, all four trace substances were detected.

(Example 7)

In GC-VUV analysis, the fragrance composition was analyzed through GC-VUV in the same manner as in Examples 1 to 3 except that the temperature increase rate from 50 ° C to 250 ° C was adjusted to 30 ° C / min.

At this time, the spectral filter was installed in the detector and the analysis was performed by spectral filtering.

       By using a spectral filter that detects only a region corresponding to a specific wavelength, an analysis of a specific compound may be specifically performed.

For example, a spectral filter corresponding to 124-160 nm may be used to analyze aliphatic compounds, a spectral filter corresponding to 170-200 nm may be used to analyze aromatic compounds, and a conjugated aromatic compound may be analyzed. Spectral filters corresponding to 200-240 nm can be used.

In this example, a spectral filter corresponding to 177-182 nm was used for the detection of benzene compounds, and a spectral filter corresponding to 124-160 nm was used for analyzing the aliphatic compounds.

       1-Methyl-4-n-propylbenzene, 1-Methyl-4-ethylbenzene, Butyric acid methyl ester and 2-Ethylhexyl acetate were analyzed and detected.

Natural Tea Tree Spice Natural Rosemary Spice Synthetic strawberry spices 1-Methyl-4-n-
propylbenzene 1-Methyl-4-ethylbenzene Butyric acid methyl ester 2-Ethylhexyl acetate ○ ○ ○ ○

In Example 4, when the temperature increase rate was adjusted to 30 ℃ / min, 1-Methyl-4-n-propylbenzene, 1-Methyl-4-ethylbenzene, Butyric acid methyl ester was not detected, but by using a spectral filter 4 All compounds were detected.

Claims (4)

Sampling the perfume composition;
Supplying the sampled fragrance composition to GC-VUV;
Applying heat to the supplied perfume composition;
Injecting the heated flavor composition into a column;
Irradiating ultraviolet rays to the fragrance composition passing through the column to excite; And
In the trace material analysis method of the fragrance composition comprising the step of analyzing the excited fragrance composition,
The step of applying the heat is maintained for 1 to 10 minutes at 50 ℃, heat is applied at a temperature rising rate of 10 to 25 ℃ / min from 50 ℃ to 250 ℃, and then maintained at 250 ℃ 1 to 10 minutes, 250 Heat was applied at a temperature increase rate of 10-25 ℃ / min from ℃ to 320 ℃, then held for 1 to 10 minutes at 320 ℃,
The trace substance is 2-ethylhexylacetate, 1-methyl-4-n-propylbenzene, 1-methyl-4-ethylbenzene, and 1-Methyl- 4-ethylbenzene) and butyric acid methyl ester (butyric acid methyl ester), characterized in that at least any one of the fragrance composition analysis method.
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