Green preparation method of safe and non-irritant essence for children products

Abstract

The invention belongs to the technical field of essence preparation, and discloses a green preparation method of safe and non-irritating essence for children products, which comprises the following steps: a) extracting aromatic plant raw materials by using a natural deep eutectic solvent (NADES) at 30-45 DEG C, the NADES being selected from lactic acid, glycerol and water in a ratio of 1: 2: 1 or choline chloride and glycerol in a molar ratio of 1: 2 and containing 10-20% of water; b) selectively removing aldehydes and peroxide / epoxidation by-products from the extracting solution obtained in the step a) through an adsorption microbead layer which is formed by crosslinking chitosan through genipin and has the primary amine density of 0.8-2.0 mmol / g at the temperature of 20-30 DEG C; and c) forming an inclusion compound from the aroma component treated in the step b) and beta and / or gamma-cyclodextrin according to a mass ratio of 1: (6-12), thereby obtaining the water-dispersible essence. According to the method, NADES low-temperature extraction and glycosaminoglycan selective aldehyde removal are connected in series, then cyclodextrin immobilization and controlled release are carried out, the aldehyde removal contact and mass transfer efficiency is improved, aldehyde is directionally removed, stimulation is reduced, the microbeads can be recycled, and a green closed loop is formed.

Description

Technical Field

[0001] This invention belongs to the field of fragrance preparation technology, specifically relating to a green preparation method for safe and non-irritating fragrances for children's products. Background Technology

[0002] As consumers become increasingly concerned about the safety of children's products, the fragrance ingredients in these products are required to be milder and non-irritating. Traditional fragrances are mostly composed of chemically synthesized flavorings and solvents, and may contain ingredients that can irritate the skin or respiratory tract, such as aldehydes, ketones, and certain volatile organic compounds (VOCs). This may pose a potential hazard to children's skin and respiratory system.

[0003] Therefore, developing a fragrance specifically for children that can maintain fragrance longevity while being non-irritating and safe has become an urgent problem for the fragrance industry. Summary of the Invention

[0004] To overcome the above-mentioned technical problems, the present invention provides a green preparation method for safe and non-irritating fragrances for children's products.

[0005] The present invention adopts the following technical solution:

[0006] A green preparation method for safe and non-irritating fragrances for children's products includes the following steps:

[0007] a) Extracting aromatic plant materials with natural deep eutectic solvent (NADES) at 30–45°C, wherein the NADES is selected from lactic acid:glycerol:water = 1:2:1 or choline chloride:glycerol (molar ratio 1:2, containing 10–20% water);

[0008] b) The extract obtained in step a) is passed through an adsorption microbead layer formed by cross-linking chitosan with genipin and having a primary amine density of 0.8–2.0 mmol / g at 20–30 °C to selectively remove aldehydes and peroxide / epoxidation byproducts.

[0009] c) The aroma components treated in step b) are combined with β and / or γ-cyclodextrin at a mass ratio of 1:(6–12) to form an inclusion complex, thereby obtaining a water-dispersible fragrance;

[0010] The final product contains less than 5 ppm of total aldehyde allergens and less than 1 ppm of any monomer, and the maximum headspace release rate is reduced by ≥30% compared to the unencapsulated product.

[0011] Preferably, the microspheres in step b) are operated at pH 5.5–6.0 and a linear velocity of 0.5–2 BV / h, and the breakthrough criterion is the DNPH-aldehyde colorimetric A of the effluent. 360 Increase to 20% of the sample volume.

[0012] Preferably, in step c), maltodextrin (3–8%) is added and spray-dried to obtain a fine powder, D 50 It is 3–20 μm.

[0013] Preferably, the product further includes step d): glycosylation of linalool / geraniol using β-glucosyltransferase at pH 5.0–5.5, 35–40°C, and 30–50% (w / w) sucrose to generate the corresponding glucosinolate pro-fragrance, which accounts for 20–60% of the target terpene molar ratio in the finished product.

[0014] The present invention also discloses a water-dispersible flavoring for children prepared by any of the above methods.

[0015] Preferably, the total aldehyde content is <5 ppm, the peroxide value is <2 meq / kg, the cyclodextrin inclusion rate is ≥70%, and the maximum headspace release rate is ≥30% lower than that of the unincluded control.

[0016] The present invention also discloses the application of the above-mentioned fragrance in children's skin contact products, including shampoo and wipes, with a concentration of 0.05–0.1% (w / w).

[0017] Compared with the prior art, the beneficial effects of the present invention are:

[0018] This invention combines low-temperature NADES extraction (reducing nascent oxides) with selective aldehyde removal from aminopolysaccharides (chitosan-genipin microbeads), followed by cyclodextrin immobilization and controlled release, with defined quantitative thresholds and process windows. This is not a simple, arbitrary combination, but rather:

[0019] NADES maintains a hydrophilic-lipophilic microenvironment, improving the efficiency of aldehyde removal contact and mass transfer.

[0020] Chitosan primary amine achieves "directional removal" of aldehydes through chemoselectivity (Schiff base), which is superior to the non-selective adsorption of activated carbon;

[0021] Cyclodextrin immobilization flattens the residual volatility peak, further reducing immediate stimulation.

[0022] This solution reduces aldehyde content to ppm levels and significantly lowers headspace peaks while maintaining almost no change in aroma; moreover, the microbeads are recyclable, forming a green closed loop.

[0023] Enzymatic pre-fragrance conversion transforms some of the easily irritating free terpenoids into water-soluble, mild precursors, which are released slowly only during use, further enhancing the safety margin. Detailed Implementation

[0024] The embodiments of the present invention are described in detail below. Unless otherwise specified, the raw materials and equipment used can be purchased from the market or are commonly used in the art. The methods in the embodiments, unless otherwise specified, are conventional methods in the art. The embodiments described below are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention.

[0025] Example 1 (Formaldehyde Removal and Sensitization + Immobilized Controlled Release Type)

[0026] Raw materials and reagents

[0027] Plants: 200g crushed sweet orange peel, 50g dried Roman chamomile flowers

[0028] NADES: Lactic acid: Glycerin: Water = 1:2:1 (molar ratio), prepared to a total volume of 450g.

[0029] Chitosan-genipin microbeads: Chitosan (degree of deacetylation ≥ 85%), genipin; approximately 200 mL of wet beads were prepared, with a dry amine density ≈ 1.2 mmol / g.

[0030] Food and pharmaceutical grade β-cyclodextrin, maltodextrin (DE10)

[0031] Analysis: GC-MS, DNPH-aldehyde colorimetric reagent, peroxide value determination reagent

[0032] step

[0033] NADES extraction: The plant and NADES were mixed at a solid-liquid ratio of 1:2.5 and magnetically stirred at 35°C for 4 hours; the mixture was then filtered, and the residue was washed once with an equal amount of NADES. The filtrates were combined, yielding approximately 420 mL.

[0034] Preparation of adsorption microbeads: 2.0 g of chitosan was dissolved in 100 mL of 1% acetic acid, and 1% sodium tripolyphosphate (TPP) was added dropwise to form gel beads. The beads were washed with water until neutral. The beads were crosslinked in 0.5 mg / mL genipin aqueous solution at 25 °C for 12 h to obtain blue-green elastic beads, which were then washed and set aside for use.

[0035] Selective aldehyde / peroxide removal: Adjust the pH of the extract to 5.8 (lactic acid / NADES is usually in this range), pass it through a glass column packed with microbeads at a rate of 0.8 BV / h (bed volume BV = 200 mL), and collect the eluent; monitor A using the DNPH method. 360 The penetration point is A. 360 Stop when ≥20% of the sample has been injected.

[0036] Aromatic components were recovered: the NADES activity was reduced by diluting with an equal volume of deionized water, and some of the solvent was recovered by rotary evaporation under reduced pressure at 40°C to obtain a concentrated aroma phase, approximately 60g of viscous liquid.

[0037] Cyclodextrin inclusion: β-cyclodextrin was dissolved in water at 45°C (10%, w / w), and the concentrate from the previous step was slowly added. The aroma ratio of β-CD was 1:8 (w / w), and the mixture was stirred for 2 hours. 5% (w / w, based on slurry) of maltodextrin was added as a wall material additive.

[0038] Drying: Spray drying (inlet air 160℃ / outlet air 75–80℃) or freeze drying yields approximately 40–55g of white to pale yellow powder.

[0039] index:

[0040] GC-MS: Citral (geranial + neral) <1 ppm; Limonene oxide <1 ppm; The total peak area of ​​the main peaks (hesperidin / isoamyl isovalerate, etc.) decreased by <10% compared with before impurity removal.

[0041] Peroxide value: <2 meq / kg;

[0042] Release rate: The maximum peak height of headspace GC decreased by approximately 40–55% compared to the non-inclusion control.

[0043] Application and blending: The micro powder was added to the children's shampoo base system at 0.1% (w / w). It was stable for 24 hours with no visible oil separation. Patch test (volunteer n=10, closure after 24 hours) showed no erythema ≥ grade 1 reaction.

[0044] Microbead regeneration: Soak in 0.5% citric acid aqueous solution for 30 min to remove Schiff base conjugates; wash with water until neutral, can be reused ≥10 times, with adsorption capacity decrease of <15%.

[0045] Example 2 (Enzymatic pre-fragrance treatment + aldehyde removal + γ-CD controlled-release type)

[0046] Raw materials and reagents

[0047] Essential oil / ingredients: 150g lavender flower spikes, 80g rosewood shavings

[0048] NADES: Choline chloride:glycerol = 1:2 (molar ratio), with 15% water (w / w), total amount 400g, food-grade β-glucosyltransferase powder 500U / g

[0049] sucrose

[0050] Chitosan-genipin microbeads, prepared as above.

[0051] γ-Cyclodextrin

[0052] Analysis as above

[0053] step

[0054] NADES extraction: 40℃, 3h, solid-liquid ratio 1:2.5; filter and combine the filtrates.

[0055] Enzymatic "pre-fragrance" conversion: Take 100g of filtrate, dilute with deionized water to a total terpene alcohol concentration of approximately 0.5% (w / w), add 40% (w / w) sucrose, pH 5.2 (citric acid-citric acid buffer), add 100U / 100g of transferase at 35℃, and react for 6h; HPLC monitoring shows that the molar ratio of target glucosides generated reaches approximately 40% of the original terpene alcohols, and the reaction is terminated (60℃ for 10min).

[0056] De-aldehyde / peroxide removal: Pass the entire batch of extract (including the enzyme reaction portion) through a chitosan-genipin microbead column (pH 5.5–6.0, 1 BV / h) until the DNPH breakthrough criterion is reached.

[0057] Cyclodextrin immobilization: Inclusion with γ-cyclodextrin at an aroma:γ-CD ratio of 1:10 (w / w), stirred at room temperature for 3 hours; freeze-dried to obtain approximately 38–50 g of micro powder.

[0058] index:

[0059] GC-MS: Linalool <0.5ppm; Geraniol <1ppm;

[0060] HPLC: The total molar fraction of linalool glucoside / geraniol glucoside is approximately 40%.

[0061] Headspace release: Peak value reduced by ≥45%, release half-life extended by approximately 1.6 times.

[0062] Application: Added at 0.08% (w / w) to the wet wipes water formula, with no turbidity / layering in stability (accelerated at 45℃ for 14 days); the scent is a soft floral fragrance with a significantly reduced subjective pungent odor.

[0063] The fragrances prepared in the two examples were tested.

[0064]

[0065] Aroma evaporation rate:

[0066] The evaporation behavior of the fragrances was determined by headspace GC-MS, showing that the evaporation rates of the fragrances in Examples 1 and 2 were significantly reduced, by 45% and 50%, respectively. This means that the fragrances evaporated more slowly than the unencapsulated control sample, thereby reducing the instantaneous concentration of the aroma and minimizing skin irritation.

[0067] Total aldehyde content:

[0068] The aldehyde content in the fragrance was determined using the DNPH method. The results showed that the total aldehyde content in both examples was below 1 ppm, far below the standard requirement of 5 ppm. This meets the safety standards for low irritation and low allergenicity.

[0069] Peroxide value:

[0070] The peroxide content of the flavoring was determined by iodometric titration. The peroxide values ​​of Examples 1 and 2 were both below 2 meq / kg, indicating that no excessive peroxides were produced in the flavoring, meeting the green and low-oxidation standards.

[0071] Skin irritation:

[0072] After a 24-hour patch test (n=10 volunteers), neither of the fragrances in the two examples caused any skin erythema, edema, or itching, and both were rated as level 0, indicating that the fragrances are safe for use in children's skin contact and will not cause allergic reactions or irritation.

[0073] Pre-glycosylation body-shaping effect:

[0074] The glycosylation rates of linalool and geraniol were determined by HPLC, and the results showed that the glycosylation rate in the examples reached 40%. This means that these volatile terpenoid alcohols have been successfully converted into glycosylated precursors, which can slowly release fragrance through skin microbial enzymes during use, further reducing allergenicity and irritation.

[0075] Although embodiments of the present invention have been shown and described, those skilled in the art will understand that various changes, modifications, substitutions and variations can be made to the above embodiments without departing from the principles and spirit of the present invention, the scope of which is defined by the claims and their equivalents.

Claims

1. A green preparation method for safe and non-irritating fragrances for children's products, characterized in that, Includes the following steps: a) Extracting aromatic plant materials with natural deep eutectic solvent (NADES) at 30–45°C, wherein the NADES is selected from lactic acid:glycerol:water = 1:2:1 or choline chloride:glycerol (molar ratio 1:2, containing 10–20% water). b) The extract obtained in step a) is passed through an adsorption microbead layer formed by chitosan cross-linking with genipin and having a primary amine density of 0.8–2.0 mmol / g at 20–30°C to selectively remove aldehydes and peroxide / epoxidation byproducts. c) The aroma components treated in step b) are combined with β and / or γ-cyclodextrin at a mass ratio of 1:(6–12) to form an inclusion complex, thereby obtaining a water-dispersible fragrance; The final product contains less than 5 ppm of total aldehyde allergens and less than 1 ppm of any monomer, and the maximum headspace release rate is reduced by ≥30% compared to the unencapsulated product.

2. The green preparation method for safe and non-irritating fragrances for children's products according to claim 1, characterized in that, Step b) The microspheres were operated at pH 5.5–6.0 and a linear velocity of 0.5–2 BV / h, with the breakthrough criterion being the DNPH-aldehyde colorimetric A of the effluent. 360 Increase to 20% of the sample volume.

3. The green preparation method for safe and non-irritating fragrances for children's products according to claim 1, characterized in that, In step c), add maltodextrin (3–8%) and spray-dry to obtain a fine powder. 50 It is 3–20µm.

4. The green preparation method for safe and non-irritating fragrances for children's products according to claim 1, characterized in that, It also includes step d): glycosylation of linalool / geraniol using β-glucosyltransferase under conditions of pH 5.0–5.5, 35–40°C, and 30–50% (w / w) sucrose to generate the corresponding glucosinolate pro-fragrance, which accounts for 20–60% of the target terpene molar ratio in the finished product.

5. A water-dispersible flavoring for children prepared by any one of claims 1–4.

6. The water-dispersible flavoring for children according to claim 5, characterized in that: Total aldehydes <5ppm, peroxide value <2meq / kg, cyclodextrin inclusion rate ≥70%, and maximum headspace release rate ≥30% lower than the non-inclusion control.

7. The use of the fragrance of claim 5 in children's skin contact products, wherein the products include washes and wipes, and the concentration used is 0.05–0.1% (w / w).

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