A flavor composition for inhibiting oxidation and browning of natural flavors and maintaining odor stability and use thereof

Abstract

The application relates to a fragrance composition for inhibiting oxidation and browning of natural spices and keeping odor stability and application thereof, relates to the technical field of spices, and the composition comprises 10-80% of natural spices in mass percentage, 0.01-2% of an antioxidant component, 0.01-1% of a light stabilizing component, 0.001-0.1% of a metal ion chelating component and a solvent system. After accelerated storage of the composition at 40 DEG C + / - 2 DEG C and 75% + / - 5% of relative humidity for 12 weeks, the peak area retention rate of main aroma components in gas chromatography-mass spectrometry is not less than 80%. Through the ternary synergy of antioxidation, light stabilization and metal ion chelation, the oxidation discoloration and odor deterioration of the natural spices are significantly inhibited, the composition can be widely applied to products such as perfume, fragrance spray, shower gel and scented candle, the shelf life is prolonged, and the aroma authenticity is kept.

Description

Technical Field

[0001] This application relates to the field of fragrance technology, and in particular to a fragrance composition that inhibits the oxidation and browning of natural fragrances and maintains stable odor, and its application. Background Technology

[0002] Natural fragrances are the core scenting ingredients in perfumes, fragrances, and space fragrance products. They are derived from plant essential oils and extracts and typically contain a variety of volatile aromatic substances such as terpenes, alcohols, aldehydes, and phenols. Natural fragrances can give products rich, three-dimensional, and natural scent layers, thus holding an irreplaceable position in high-end fragrance products.

[0003] However, natural fragrances exhibit significant stability issues during actual storage and use. These issues primarily manifest in the following ways: First, volatile components are prone to oxidative degradation in the presence of air, light, and trace metal ions, leading to a decrease in aroma intensity. Second, different components degrade at inconsistent rates, disrupting the original aroma structure and resulting in odor shifts or unpleasant off-odors. Third, oxidation products are accompanied by color changes, with the product gradually changing from colorless or pale yellow to yellow or even brown, severely impacting its appearance and quality.

[0004] To address these issues, current technologies commonly employ the addition of a single antioxidant to the fragrance system, such as butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), or tocopherol. However, single antioxidants only inhibit free radical chain reactions and have limited effectiveness against deterioration pathways such as photoinduced degradation and metal ion-catalyzed oxidation. Some antioxidants themselves possess odors, which, at high concentrations, can easily interfere with the original aroma of natural fragrances. Furthermore, current technologies lack effective methods for quantitatively evaluating aroma stability, making objective comparisons between different studies difficult.

[0005] Therefore, there is an urgent need to provide a multi-component synergistic fragrance stabilizing composition to improve the application quality of natural fragrances in daily chemical products. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a fragrance composition that inhibits the oxidation and browning of natural fragrances and maintains the stability of the aroma, and its application. It solves the technical problem that existing fragrance stabilization technologies are unable to simultaneously inhibit the oxidation, photodegradation and metal catalytic deterioration of natural fragrances.

[0007] To achieve the above objectives, the present invention provides the following technical solution: A fragrance composition that inhibits the oxidation and browning of natural fragrances and maintains odor stability, and its application therein, comprising: Natural fragrance components, wherein the natural fragrances constitute 10%-80% by mass of the composition; An antioxidant component, wherein the antioxidant component constitutes 0.01%-2% of the composition by mass. A light-stabilizing component, wherein the light-stabilizing component comprises 0.01%-1% by mass in the composition; A metal ion chelating component, wherein the metal ion chelating component constitutes 0.001%-0.1% of the composition by mass. and solvent systems; After the composition was stored at 40℃±2℃ and 75%±5% relative humidity for 12 weeks, the peak area retention rate of the main aroma components was not less than 80% and the overall color difference ΔE was not higher than 3 when detected by gas chromatography-mass spectrometry.

[0008] Furthermore, the natural fragrance is selected from one or more of citrus essential oils, floral essential oils, herbal essential oils, or resinous essential oils; the natural fragrance contains one or more easily oxidized components selected from limonene, linalool, citronellol, geraniol, α-pinene, β-caryophyllene, or citral.

[0009] Furthermore, the antioxidant component is selected from one or more of tocopherol, butylated hydroxytoluene, butylated hydroxyanisole, or ascorbyl palmitate; the photostable component is selected from one or more of benzophenone, benzotriazole, or cinnamic acid ester ultraviolet absorbers; and the metal ion chelating component is selected from one or more of ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetic acid, tetrasodium ethylenediaminetetraacetic acid, citric acid, or phytic acid.

[0010] Furthermore, the mass ratio of the antioxidant component to the photostable component is 1:0.1-1:2, the mass ratio of the metal ion chelating component to the antioxidant component is 1:10-1:200, and the total mass percentage of the antioxidant component, photostable component and metal ion chelating component does not exceed 3% of the total mass of the composition.

[0011] Furthermore, the solvent system is selected from one or more of ethanol, propylene glycol, dipropylene glycol, or isopropyl myristate.

[0012] Furthermore, the gas chromatography-mass spectrometry (GC-MS) detection conditions are as follows: the chromatographic column is a DB-5MS or equivalent column, with a column length of 30 m, an inner diameter of 0.25 mm, and a film thickness of 0.25 μm; the carrier gas is helium, with a flow rate of 1.0 mL / min; the temperature program is from 60 °C to 280 °C at a rate of 5 °C / min; the mass spectrometer uses an electron impact ionization source with an ionization energy of 70 eV and a scan range of m / z 35-450. The peak area retention rate is calculated as follows: using n-dodecane or n-hexadecane as internal standards, the peak areas of each major aroma component are extracted and calculated according to the following formula: Where A represents the corrected peak area of ​​the main aroma components before accelerated storage, and A represents the corrected peak area of ​​the same components after accelerated storage.

[0013] Furthermore, the overall color difference ΔE is determined according to the CIELAB color space and calculated using the following formula: Where ΔL , Δa Δb These represent the differences in brightness, red-green tint, and yellow-blue tint of the samples before and after storage.

[0014] Furthermore, when the composition does not contain either the light-stabilizing component or the metal ion chelating component, under the same accelerated storage conditions, the peak area retention rate of the main aroma component is reduced to below 65%, and the overall color difference ΔE is greater than or equal to 6.

[0015] Furthermore, after the composition is stored at room temperature and away from light for 6 months, the peak area retention rate of the main aroma components is not less than 85%, and the overall color difference ΔE is not higher than 2.

[0016] The use of the fragrance composition according to any one of the above-mentioned methods in the preparation of perfumes, eau de toilettes, fragrance sprays, shower gels, space fragrance products or scented candles.

[0017] In summary, this application includes at least one fragrance composition that inhibits the oxidation and browning of natural fragrances and maintains odor stability, as well as its application and methods, which offer the following beneficial technical effects: 1. This invention utilizes a ternary synergistic system of antioxidant components, photostable components, and metal ion chelating components to simultaneously block three degradation pathways in natural fragrances—free radical chain oxidation, photo-induced excited-state reactions, and transition metal-catalyzed autoxidation—at extremely low dosages of each component. When all three are present, it solves the problem of odor distortion and color difference caused by the inability of a single antioxidant to simultaneously inhibit photo-oxidation and metal-catalyzed oxidation. 2. By limiting the mass ratio of antioxidant components to light-stabilizing components to 1:0.1-1:2, and the mass ratio of metal ion chelating components to antioxidant components to 1:10-1:200, the decrease in solvent solubility and changes in fragrance texture caused by excessive addition of light stabilizers or chelating agents are reduced, meeting the stringent industry requirements for the safety of additives in fragrance products, and achieving a balance between high stability and high safety. 3. Under the protection of the composition, the fragrance composition, after being stored at room temperature and away from light for 6 months, is significantly superior to natural fragrances without the addition of this composition. It can be directly used to prepare end products such as perfumes, eau de toilette, fragrance sprays, shower gels, space fragrances, and scented candles, without the need for additional preservatives or special packaging treatments, greatly reducing the shelf-life management costs of the products. Detailed Implementation

[0018] To facilitate a clear understanding of the technical means, creative features, objectives, and effects of this invention, the invention will be further described below in conjunction with specific embodiments.

[0019] This application discloses a fragrance composition that inhibits the oxidation and browning of natural fragrances and maintains stable odor, and its application.

[0020] In the following examples and comparative examples, stability tests were conducted according to the conditions described in claim 1: the test compositions were stored in a constant temperature and humidity chamber at 40℃±2℃ and 75%±5% relative humidity for 12 weeks, and samples were taken before and after storage. Aroma component analysis was performed using gas chromatography-mass spectrometry (GC-MS) under the following conditions: the chromatographic column was a DB-5MS (30 m × 0.25 mm × 0.25 μm), the carrier gas was helium, the flow rate was 1.0 mL / min, and the temperature program started at 60℃ and increased to 280℃ at a rate of 5℃ / min; the mass spectrometry used an electron impact ion source (70 eV), with a scan range of m / z 35~450. Using n-dodecane as an internal standard, the peak area retention rates of each major aroma component were calculated according to the formula in claim 6. Each sample was measured in triplicate, and the average value of the results was taken.

[0021] Example 1 This embodiment provides a fragrance composition that inhibits the oxidation and browning of natural fragrances and maintains stable odor. Its composition is as follows: the natural fragrance component is sweet orange essential oil (the main easily oxidized component is limonene, with a GC-MS content of approximately 65%, an acid value of 0.8 mg KOH / g, and a peroxide value of 2.3 meq / kg), accounting for 40% by mass in the composition; the antioxidant component is tocopherol (>96%, naturally sourced), at 0.5%; the photostable component is benzophenone-3 (2-hydroxy-4-methoxybenzophenone, UV absorption range 290-350 nm), at 0.2%; the metal ion chelating component is disodium ethylenediaminetetraacetate (EDTA), at 0.01%; and the solvent system is propylene glycol (purity ≥99.5%), made up to 100%. The mass ratios of the above components meet the following requirements: antioxidant component: light stabilizer component = 1:0.4, metal ion chelating component: antioxidant component = 1:50, and the total mass percentage of the three components is 0.71%, which is significantly lower than 3% of the total mass of the composition, thus meeting the safety weight limit requirements for additives in daily chemical products.

[0022] The preparation was carried out at room temperature (22℃±2℃), normal pressure, and under conditions avoiding direct sunlight. The specific steps are as follows: (1) Add the prescribed amount of disodium EDTA to propylene glycol and stir with a magnetic stirrer at 200 rpm for 10 minutes until completely dissolved to obtain a clear solution A; (2) Add tocopherol and benzophenone-3 to solution A, and continue stirring for 15 minutes until the system is homogeneous and transparent to obtain solution B; (3) Under stirring conditions (300 rpm), sweet orange essential oil is slowly added dropwise to solution B at a rate of about 2 mL / min, and the system temperature is kept below 30℃ during the addition process; (4) After the addition is complete, continue stirring at 200 rpm for 15 minutes to obtain a uniform, transparent, light yellow liquid.

[0023] Following the above testing method, tests were conducted after 12 weeks of accelerated storage. The results showed: The peak area retention rate of the main aroma component limonene was (87.3 ± 1.2)%, the retention rate of linalool (a trace component naturally present in sweet orange essential oil, with a content of about 0.8%) was (91.2 ± 0.9)%, and the overall color difference ΔE = 1.8 ± 0.2.

[0024] Sensory evaluation results: Aroma intensity retention rate 82%, aroma characteristic deviation score 4.2 / 5 (virtually no deviation), off-odor intensity score 1.5 / 5 (almost no off-odor). After storage, the sample still retains the sweet citrus characteristic aroma, without obvious turpentine, metallic or rancid odors caused by oxidation, and the color changes slightly from light yellow to pale yellow.

[0025] Example 2 The difference between this embodiment and Embodiment 1 lies in the types and amounts of natural fragrances used. The specific composition is as follows: The natural fragrance uses lavender essential oil (the main easily oxidized components are linalool and linalyl acetate), accounting for 60% by mass; the antioxidant component is butylated hydroxytoluene (BHT), accounting for 0.8%; the photostable component is octocrylene (2-cyano-3,3-diphenylacrylate-2-ethylhexyl ester), accounting for 0.5%; the metal ion chelating component is citric acid (anhydrous grade), accounting for 0.02%; the solvent system is dipropylene glycol, made up to 100%. The above components satisfy the following ratios: antioxidant component: photostable component = 1:0.625, metal ion chelating component: antioxidant component = 1:40, and the total mass percentage of the three is 1.32%. The preparation method is the same as in Example 1.

[0026] It should be noted that in the dipropylene glycol system, the measured water content is 0.12% to 0.18% (Karl Fischer method). This trace amount of water is sufficient to support the partial ionization of citric acid, thereby enabling its chelation effect on trace metal ions.

[0027] After 12 weeks of accelerated storage using the aforementioned method, the peak area retention rates of the main aroma components were as follows: linalool 85.6%, linalyl acetate 82.9%, and overall color difference ΔE = 2.3. The sample color slightly deepened from pale yellow to light yellow, with the color difference within an acceptable range. Sensory evaluation results showed that the sample retained the characteristic green and floral aroma of lavender, with no obvious aldehyde pungent odor detected (odor intensity score ≤ 1.5 / 5), and good consistency with the aroma profile before accelerated storage.

[0028] Example 3 The difference between this embodiment and Example 1 lies in the types and amounts of natural fragrances. A compound system is used: 20% lemon essential oil and 10% frankincense essential oil (resin-based) are mixed, resulting in a total natural fragrance content of 30% by mass. The antioxidant component is a 1:1 mixture of ascorbic acid palmitate and tocopherol, with a total content of 0.3%. The light stabilizer is benzotriazole UV-P (2-(2H-benzotriazole-2-yl)-4-methylphenol), with a content of 0.3%. The metal ion chelating component is disodium calcium ethylenediaminetetraacetate (oil-dispersible type), with a content of 0.005% (based on active ingredient). The solvent system is isopropyl myristate (IPM), made up to 100%. The above components satisfy the following ratios: antioxidant component:light stabilizer component = 1:1, metal ion chelating component:antioxidant component = 1:60, and the total mass percentage of the three is 0.605%.

[0029] In preparation, calcium disodium EDTA and isopropyl myristate, which are 20 times their weight, are ultrasonically dispersed at 60°C for 5 minutes to form a uniform dispersion. After cooling to room temperature, ascorbyl palmitate, tocopherol, UV-P and the remaining solvent are added in sequence and stirred until completely dissolved (about 15 minutes). Finally, a premix of lemon essential oil and frankincense essential oil is slowly added dropwise while stirring at 300 rpm, and stirring is continued for 15 minutes to obtain a uniform, transparent, pale yellow liquid.

[0030] After 12 weeks of accelerated storage using the aforementioned method, the following results were obtained: limonene retention rate was 89.4%, α-pinene (a representative easily oxidized component found in both lemon essential oil and frankincense essential oil) retention rate was 88.1%, and the overall color difference ΔE = 1.5.

[0031] After being stored at room temperature and protected from light for 6 months (25℃±2℃, relative humidity 60%±10%), the composition was retested, and the limonene retention rate was 87.2%, ΔE=1.9. As a control, a composition using the same blend of natural flavorings but without any stabilizing components (diluted only with isopropyl myristate to the same concentration) showed a limonene retention rate of only 34.2% and an α-pinene retention rate of 29.6% after 6 months of storage under the same conditions, ΔE=8.7, and exhibited obvious precipitation and a rancid odor.

[0032] Sensory evaluation results showed that the sample in this embodiment retained the citrus-resin aroma characteristics of lemon and frankincense complex after 6 months of storage, without significant oxidation-induced turpentine, rancidity, or metallic off-odors (off-odor intensity score ≤ 1.0 / 5), and the aroma profile consistency score was 4.5 / 5. All of the above data met the thresholds set in claim 9 (retention rate ≥ 85%, ΔE ≤ 2), confirming the effectiveness of the stable system of the present invention under long-term storage conditions.

[0033] Comparative Example 1 This comparative example illustrates the effect of missing light-stabilizing components. The composition is the same as in Example 1, but the light-stabilizing component benzophenone-3 is removed, and the amount of propylene glycol is increased accordingly to make up 100%, while the remaining components and their amounts remain unchanged.

[0034] After 12 weeks of accelerated storage, the peak area retention of limonene decreased to 58.4%, the retention of linalool decreased to 61.7%, and the overall color difference ΔE = 6.8. The sample color darkened significantly to orange-red and was accompanied by a strong oxidative odor, which did not meet the requirements of claim 1 for a retention rate ≥ 80% and ΔE ≤ 3.

[0035] Comparative Example 2 This comparative example illustrates the effect of missing metal ion chelating components. The composition is the same as in Example 1, except that disodium EDTA is omitted and propylene glycol is added.

[0036] After 12 weeks of accelerated storage, the limonene retention rate was 62.3%, ΔE=6.1. Although the presence of the light stabilizer delayed some photo-oxidation, the retention rate and color difference were still far inferior to those in Example 1 due to the trace metal ions inevitably present in natural essential oils, mainly from plant materials and containers, undergoing catalytic auto-oxidation.

[0037] Comparative Example 3 This comparative example illustrates the case where both the photostable component and the metal ion chelating component are missing, but the antioxidant component is retained. The composition is the same as in Example 1, except that 0.5% tocopherol is retained, benzophenone-3 and disodium EDTA are removed, and propylene glycol is added to make up the difference.

[0038] After 12 weeks of accelerated storage, the limonene retention rate was only 41.5%, ΔE=9.3, and the sample showed severe browning and precipitation. This result is consistent with the description in claim 8, demonstrating that a single antioxidant component cannot effectively protect natural fragrances under humid, hot, and light conditions.

[0039] Table 1. Composition and post-storage test results of Examples 1-3 and Comparative Examples 1-3 In Examples 1–3, the peak area retention rates of the main aroma components in all compositions were not less than 82%, with the lowest being 82.9% for linalyl acetate in Example 2, and ΔE not exceeding 2.3, fully satisfying the thresholds of 80% and ΔE ≤ 3 in Claim 1. The retention rates of Comparative Examples 1–3 were all below 65%, with ΔE ≥ 6.1, consistent with the expected results described in Claim 8, confirming that the antioxidant-photostabilized-metal ion chelating ternary system of the present invention is indispensable and exhibits a clear synergistic effect.

[0040] Comparative Example 4 To simulate the actual shelf life performance of the product, the composition of Example 1, the blank control group, and the composition of Comparative Example 1 were stored simultaneously at room temperature and away from light (25℃±2℃, relative humidity 60%±10%) for 6 months and tested according to the requirements of claim 9.

[0041] Table 2. Stability comparison after 6 months of long-term room temperature storage The composition of this invention (Example 1), after being stored at room temperature and away from light for 6 months, exhibits a peak area retention rate of no less than 85% (88.6% measured) for the main aroma components and a comprehensive color difference ΔE no higher than 2 (1.5 measured), fully meeting the requirements of claim 9. In contrast, compositions lacking any key component (such as Comparative Example 1) or without any added stabilizer (blank control group) struggle to meet basic quality requirements even under room temperature storage conditions alone. This demonstrates that the technical solution of this invention is not only suitable for accelerated aging tests but also effectively ensures the aroma and color stability of the product during its actual shelf life.

[0042] The above are all preferred embodiments of this application, and are not intended to limit the scope of protection of this application. Therefore, all equivalent changes made in accordance with the structure, shape and principle of this application should be covered within the scope of protection of this application.

Claims

1. A fragrance composition that inhibits the oxidation and browning of natural fragrances and maintains odor stability, characterized in that, include: Natural fragrance components, wherein the natural fragrances constitute 10%-80% by mass of the composition; An antioxidant component, wherein the antioxidant component constitutes 0.01%-2% of the composition by mass. A light-stabilizing component, wherein the light-stabilizing component comprises 0.01%-1% by mass in the composition; A metal ion chelating component, wherein the metal ion chelating component constitutes 0.001%-0.1% of the composition by mass. and solvent systems; After the composition was stored at 40℃±2℃ and 75%±5% relative humidity for 12 weeks, the peak area retention rate of the main aroma components was not less than 80% and the overall color difference ΔE was not higher than 3 when detected by gas chromatography-mass spectrometry.

2. The fragrance composition according to claim 1, which inhibits the oxidation and browning of natural fragrances and maintains odor stability, is characterized in that... The natural fragrance is selected from one or more of citrus essential oils, floral essential oils, herbal essential oils, or resinous essential oils; the natural fragrance contains one or more easily oxidized components selected from limonene, linalool, citronellol, geraniol, α-pinene, β-caryophyllene, or citral.

3. The fragrance composition according to claim 1, which inhibits the oxidation and browning of natural fragrances and maintains odor stability, is characterized in that... The antioxidant component is selected from one or more of tocopherol, butylated hydroxytoluene, butylated hydroxyanisole, or ascorbyl palmitate; the photostable component is selected from one or more of benzophenone, benzotriazole, or cinnamic acid ester ultraviolet absorbers; and the metal ion chelating component is selected from one or more of ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetic acid, tetrasodium ethylenediaminetetraacetic acid, citric acid, or phytic acid.

4. The fragrance composition according to claim 1, which inhibits the oxidation and browning of natural fragrances and maintains odor stability, is characterized in that... The mass ratio of the antioxidant component to the photostable component is 1:0.1-1:2, the mass ratio of the metal ion chelating component to the antioxidant component is 1:10-1:200, and the total mass percentage of the antioxidant component, photostable component and metal ion chelating component does not exceed 3% of the total mass of the composition.

5. The fragrance composition according to claim 1, which inhibits the oxidation and browning of natural fragrances and maintains odor stability, is characterized in that... The solvent system is selected from one or more of ethanol, propylene glycol, dipropylene glycol, or isopropyl myristate.

6. The fragrance composition according to claim 1, which inhibits the oxidation and browning of natural fragrances and maintains odor stability, is characterized in that... The gas chromatography-mass spectrometry (GC-MS) detection conditions were as follows: the chromatographic column was a DB-5MS or equivalent column, 30 m long, 0.25 mm inner diameter, and 0.25 μm film thickness; the carrier gas was helium, with a flow rate of 1.0 mL / min; the temperature program was from 60 °C to 280 °C at a rate of 5 °C / min; the mass spectrometer used an electron impact ionization source with an ionization energy of 70 eV and a scan range of m / z 35-450. The peak area retention rate is calculated as follows: using n-dodecane or n-hexadecane as internal standards, the peak areas of each major aroma component are extracted and calculated according to the following formula: 。 Where A represents the corrected peak area of ​​the main aroma components before accelerated storage, and A represents the corrected peak area of ​​the same components after accelerated storage.

7. The fragrance composition according to claim 1, which inhibits the oxidation and browning of natural fragrances and maintains odor stability, is characterized in that... The overall color difference ΔE is determined according to the CIELAB color space and calculated using the following formula: Where ΔL , Δa Δb These represent the differences in brightness, red-green tint, and yellow-blue tint of the samples before and after storage.

8. The fragrance composition according to claim 1, which inhibits the oxidation and browning of natural fragrances and maintains odor stability, is characterized in that... When the composition does not contain either a light-stabilizing component or a metal ion chelating component, under the same accelerated storage conditions, the peak area retention rate of the main aroma components decreases to below 65%, and the overall color difference ΔE is greater than or equal to 6.

9. The fragrance composition according to claim 1 that inhibits the oxidation and browning of natural fragrances and maintains odor stability, and its application, characterized in that, After the composition is stored at room temperature and away from light for 6 months, the peak area retention rate of the main aroma components is not less than 85%, and the overall color difference ΔE is not higher than 2.

10. The use of the fragrance composition according to any one of claims 1 to 9 in the preparation of perfumes, eau de toilette, fragrance sprays, shower gels, space fragrance products or scented candles.

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