KR102562427B1 - Biodegradable fragrance compound - Google Patents

Abstract

It relates to a biodegradable perfume composition, which is smoothly degraded in a water environment due to its high biodegradability, and is not only environmentally friendly, but also has an effect of providing high fragrance satisfaction by including natural perfume.

Description

Biodegradable fragrance composition {Biodegradable fragrance compound}

It relates to a biodegradable perfume composition.

'Pharmaceuticals and Personal Care Products as Pollutants (PPcPs)' refers to many types of chemical products intended for personal health, hygiene and beauty, such as soaps, lotions, toothpastes, perfumes and sunscreens. there is These chemical components for PPcPs can cause temporary or long-term toxicity to aquatic ecosystems such as algae, fish, and daphnia living in freshwater or seawater, and are emerging as a major problem worldwide.

In particular, among PPcPs, musk-based ingredients (synthetic musk) are known as representative fragrance ingredients, and are used in cosmetics, perfumes, and household goods because of their good palatability and durability, and thousands of tons are produced worldwide every year. PPcPs chemicals, such as the Musk component, dissolve in water and accumulate in the adipose tissue of aquatic organisms, and even at low concentrations, long-term exposure to ecosystems can cause chronic or delayed adverse effects. In addition, due to the impact on the aquatic environment, it causes deformity of aquatic organisms or ecosystem disturbance.

On the other hand, research on fragrances considering the aquatic ecosystem is insignificant, and biodegradability data that decomposes in the aquatic environment is not available for all fragrance components, so it is necessary to develop a tool that can predict this and an alternative fragrance composition with high biodegradability.

One aspect is to provide a biodegradable perfume composition comprising cis-3-Hexenol, hedione and sandalore as active ingredients.

Another aspect is to provide a personal care product comprising the perfume composition.

Another aspect is to provide a home care product comprising the perfume composition.

One aspect is to provide a biodegradable perfume composition including an alcohol-type perfume including a green series and a woody-type perfume, and a ketone-type perfume. In one embodiment, a biodegradable perfume composition containing cis-3-Hexenol, hedione and sandalore as active ingredients is provided.

The perfume composition includes a "readily biodegradable" synthetic perfume.

As used herein, the term "readily biodegradable" refers to a material capable of being biodegraded by 60 to 100% in a natural state when exposed to sunlight, water, and microbial activity for 28 days. Therefore, since the composition according to one aspect is well decomposed in an aquatic environment by including a material having a biodegradability of 60 to 100%, it is possible to improve problems such as deformity of aquatic organisms or ecosystem disturbance that have occurred in existing fragrances.

As used herein, the term "alcohol flavor" is a compound having -OH (alcohol group) as a functional group, and includes green, herbal, fruity, and floral flavors. It is divided into series, woody series, etc. Specifically, the green series includes cis-3-hexenol, 2,6-nonadienol, and the like. In addition, the herb series includes terpineol, eucalyptol, and the like. In addition, the fruit flavor type includes benzyl alcohol and the like. In addition, flower fragrances include linalool, hydratropic alcohol, and the like. In addition, woody types include cedrol, vetiverol, and santalol.

As used herein, the term "ketone perfume" has a structure of r-CO-R' in which an oxygen atom double-bonded to one carbon atom and two different carbon atoms are bonded. Specifically, the ketone flavors are divided into fruity, floral, gourmand, musky, and the like. The fruit flavor series includes raspberry ketone and the like. In addition, the flower fragrance series includes dihydrojasmone and the like. In addition, the Gourmand series includes 6-acetyl-2,3,4,5-tetrahydropyridine and the like. In addition, the musk series includes must ketone and the like.

In one embodiment, the perfume composition may include 0.01 to 1.0% by weight of cis-3-hexenol, 25 to 35% by weight of hedione, and 2.0 to 5.0% by weight of sandalore, based on the total weight of the composition. there is.

The cis-3-hexenol (CAS NO. 928-96-1) smells like freshly cut grass and is a major component of the green series. The cis-3-hexenol may be included in an amount of 0.01 to 1.0% by weight based on the total weight of the composition. For example, the cis-3-hexenol is 0.01 to 1.0% by weight, 0.01 to 0.8% by weight, 0.01 to 0.7% by weight, 0.01 to 0.6% by weight, 0.01 to 0.5% by weight, 0.05 to 1.0% by weight based on the total weight of the composition % by weight, 0.05 to 0.8% by weight, 0.05 to 0.6% by weight, 0.1 to 0.8% by weight, 0.1 to 0.5% by weight or 0.3 to 0.5% by weight. At this time, when the content of cis-3-hexenol is less than the above range, there is a problem that the fragrance of fresh green feeling is reduced, and when it exceeds the above range, there is a problem that a sharp green fragrance that pierces the nose felt from the chemical component may be felt there is.

The hedione (CAS NO. 24851-98-7) is a good raw material that gives off a subtle floral scent and gives a sophisticated feel. The hedione may be included in an amount of 25 to 35% by weight based on the total weight of the composition. For example, the hedione is present in an amount of 25 to 35% by weight, 25 to 33% by weight, 25 to 31% by weight, 26 to 35% by weight, 26 to 34% by weight, 26 to 32% by weight, 27% by weight, based on the total weight of the composition. to 35% by weight, 27 to 34% by weight, 27 to 32% by weight, 29 to 34% by weight or 30 to 35% by weight. At this time, if the content of hedione is less than the above range, there is a problem that the feeling of the soft floral scent that emits fragrance is reduced, and if it exceeds the above range, the natural-friendly herbal scent to be realized cannot be sufficiently exerted. has a problem.

The sandalore (CAS NO. 65113-99-7) is a woody-based raw material, and is a raw material that is often used when trying to impart a feeling of sandalwood, and provides persistence and a warm aftertaste. The sandalore may be included in an amount of 2.0 to 5.0% by weight based on the total weight of the composition. For example, the sandalore is 2.0 to 5.0% by weight, 2.0 to 4.8% by weight, 2.0 to 4.5% by weight, 2.0 to 4.3% by weight, 2.0 to 4.0% by weight, 2.0 to 3.5% by weight or 2.0% by weight based on the total weight of the composition. to 3.0 by weight. At this time, if the content of sandalore is less than the above range, there is a problem in that the cozy and reverberation feeling is not sufficiently exhibited, and if it exceeds the above range, there is a problem that a woody fragrance may be dominant.

The perfume composition may further include a synthetic perfume. The synthetic fragrance is, for example, allyl heptanoate, nerolidol, 3-hexen-1-yl methyl carbonate, linalyl acetate ), ethyl linalool, citronellyl acetate, vanillin, phenylethyl alcohol, terpineol, ionone, and the like. The synthetic fragrance may be included in 85 to 99.9% by weight based on the total weight of the composition. For example, the synthetic fragrance is 85 to 99.9% by weight, 85 to 99% by weight, 85 to 98.5% by weight, 87 to 99.9% by weight, 88 to 99.9% by weight, 90 to 99.9% by weight, 95% by weight based on the total weight of the composition to 99.9% by weight, 96 to 99.9% by weight, 97 to 99.9% by weight or 98% by weight. At this time, if the content of the synthetic fragrance is less than the above range, there is a problem that the natural fragrance may be masked or the intensity of the fragrance may be lowered by a solvent, etc. However, there is a problem that consumer preference is low.

In another embodiment, the fragrance composition may further include a natural fragrance. The natural fragrance is, for example, grapefruit oil, geranium oil, clary sage oil, lemon oil, chamomile oil, eucalyptus oil oil) and lavender oil. The natural fragrance may be included in an amount of 0.1 to 3.0% by weight based on the total weight of the composition. For example, the natural fragrance is present in an amount of 0.1 to 3.0% by weight, 0.1 to 2.8% by weight, 0.1 to 2.5% by weight, 0.1 to 2.0% by weight, 0.5 to 3.0% by weight, 0.5 to 2.5% by weight, or 0.5% by weight based on the total weight of the composition. to 2.0% by weight or 1.0 to 2.5% by weight. At this time, when the content of the natural fragrance is less than the above range, there is a problem that the natural fragrance is not sufficiently exhibited in the natural fragrance, and when it exceeds the above range, there is a problem that the existing fragrance may be covered by the natural fragrance. In one embodiment, in the case of a composition containing synthetic fragrances, there is a problem in that synthetic fragrances do not harmonize with each other and a rough green fragrance is felt a lot, but by including natural fragrances, natural and eco-friendly feelings are increased, increasing consumer preference. And it was confirmed that the preference was increased. Therefore, the perfume composition according to one aspect may gently harmonize the rough feeling and fragrance coming from the synthetic perfume and induce a luxurious fragrance by further including the natural perfume in the synthetic perfume. In addition, it is possible to broaden the range of consumer choices by including various natural flavors.

Another aspect provides a personal care product comprising the perfume composition. Details of the perfume composition are as described above.

As used herein, the term "personal care product" refers to cosmetics applied to the body, including human and animal skin, hair, scalp and nails, hair care products, toiletries, cosmeceuticals, beauty aids, insect repellents, It means personal hygiene and cleansing products, etc., and can be applied to all personal care compositions in which fragrance is added. Such personal care compositions include, for example, deodorants, antiperspirants, sprays, stick and roll-on products, shaving products, skin lotions, moisturizers, toners, bath products, cleansers, shampoos, conditioners, combined shampoos/conditioners. , mousse, styling gel, hairspray, hair dye, hair colorant, hair bleach, waving agent, hair straightener, nail polish, nail polish remover, nail cream and lotion, keratin softener, sunscreen, insect repellent, anti-aging agent, lipstick, Foundations, face powders, eyeliners, eye shadows, blushes, makeup, mascaras, moisturizing preparations, body and hand preparations, skin care preparations, face and neck preparations, tonics, dressings, hair grooming aids, aerosol fixatives, Fragrance preparations, aftershave, make-up preparations, soft focus products, night and day skin care preparations, non-pigmented hair preparations, tanning preparations, synthetic and non-synthetic soap bars, hand liquids, nose strips, non-woven fabrics for personal care Amenities, baby lotion, baby bath and shampoo, baby conditioner, shaving aid, cucumber slice, skin pad, makeup remover, facial cleanser, cold cream, sunscreen, mousse, spritz, paste mask and mud, face mask, colo Nu and lotion, hair cuticle coat, shower gel, face and body wash, personal care rinse-off, gel, foam bath, scrubbing cleanser, astringent, nail conditioner, eyeshadow stick, face or eye powder, lip balm, lip gloss, Haircare pump sprays and other non-aerosol sprays, hair-freeze control gels, hair leave-in conditioners, hair pomades, hair detangling agents, hair fixatives, hair bleaching agents, skin lotions, preshaves and pre-electric shaves, anhydrous Creams and lotions, oil/water type, water/type, multiple macro and microemulsions, water-resistant creams and lotions, preparations for acne skin, mouthwash, massage oil, toothpaste, clear gels and sticks, ointment bases, topical wound healing agents, aerosol talc , barrier sprays, vitamins and anti-aging preparations, herbal extract preparations, bath salts, bath and body milks, hair styling aids, hair-, eye-, nail- and skin-soft products, release-controlled personal care agents , hair conditioning mists, skin care moisturizing mists, skin wipes, pore skin wipes, pore cleansers, blemish reducers, skin exfoliators, exfoliators, skin towelettes and cloths, depilatory agents, personal care lubricants and nail coloring aids, etc. can

Another aspect provides a home care product comprising the perfume composition. Details of the perfume composition are as described above.

As used herein, the term "home care products" refers to products used for household purposes for cleaning surfaces or maintaining hygiene in kitchens and bathrooms (e.g., hard surface cleaners, manual and automatic dish care, toilet bowl cleaners and disinfectants, dish detergents ), products for use in laundry products such as fabric care and cleaning (e.g., detergents, fabric softeners, pre-stain removers), fragrances that emit fragrance compounds to remove odors or in some cases are used as a substitute for perfume. and the like, and can be applied to all home care compositions into which fragrance is added. Such home care compositions include, for example, laundry detergents, laundry detergent additives, laundry bars, fabric softeners, dish detergents, wood and furniture polishes, floor polishes, bathtub and tile cleaners, toilet bowl cleaners, hard surface cleaners, window cleaners, and fogging agents. deterrents, drain cleaners, self-dishwashing and sheeting agents, carpet cleaners, prewash spotters, rust stain cleaners, scale removers, deodorants and air fresheners, and the like.

As described above, the composition according to one aspect has a high biodegradability and is smoothly degraded in a water environment, thereby being environmentally friendly. In addition, various fragrances can be configured by including various natural fragrances, and there is an effect of improving residual fragrance. Therefore, the composition according to one aspect may be applied as a flavoring agent for various products such as cosmetics, perfumes, and household goods.

The composition according to one aspect has a high degree of biodegradability and is smoothly degraded in a water environment, and is not only environmentally friendly, but also has an effect of providing high fragrance satisfaction by including various natural fragrances.

Hereinafter, a preferred embodiment is presented to aid understanding of the present invention. However, the following examples are provided to more easily understand the present invention, and the content of the present invention is not limited by the following examples.

[Preparation example]

Preparation Example 1. Selection of fragrance raw materials with high biodegradability

1-1. Relationship between Log P-value and biodegradability of fragrance

It was judged that biodegradation would be good only when the solubility in water was high, and the log P-value was selected as the first factor. The log P-value of a fragrance is a value obtained by taking log of the value representing the ratio of solubility when a single fragrance is dissolved in octanol and when dissolved in water. The higher the log P-value, the more hydrophobic the fragrance, and the lower the value, It can be said to be hydrophilic. As a result of comparing the log P-value and biodegradability of 92 frequently used single chemical fragrance ingredients, it was difficult to find a clear correlation between the two, so it could not be seen that the log P-value had an effect on biodegradability.

1-2. Relationship between chemical functional groups and biodegradability

The relationship between the chemical functional group and biodegradability, which is the second factor, was confirmed under the assumption that the more highly reactive active functional groups are included, the better the biodegradation will be. Among 92 compounds of single fragrance ingredients, molecules with benzene rings showed high biodegradability, but some exceptional cases were found, so the causal relationship between molecular structural characteristics and biodegradability could not be confirmed either.

1-3. Biodegradable Fragrance Substances according to OECD Guidelines

In order to screen raw materials with high biodegradability, values derived from experiments based on OECD guidelines were used for 121 frequently used perfume ingredients (92 chemical raw materials and 29 natural raw materials).

The OECD guidelines for biodegradability measurement basically use the 301 method, and in rare cases, biodegradability values measured through the 310 and 302 methods also exist. The types and characteristics of the OECD guideline are shown in Table 1 below.

OECD TG Test Methods note 301A Measurement of dissolved organic carbon reduction Similar to ISO standard 7827-1984 301B Carbon dioxide generation measurement 301C Oxygen uptake measurement 301D Measurement of dissolved oxygen consumption using an airtight test bottle 301E Revised OECD screening test (dissolved organic carbon reduction measurement test II) 301F Respiration measurement test using manometer Most recently devised and currently most actively used version 310 CO2 measurement test in airtight container (Headsapce test)

Since the biodegradability test method of Table 1 is a technique for measuring the amount of CO ₂ or O ₂ that is changed while microorganisms decompose the material, even if the same material is tested in the same way, the degree of biodegradability may vary to a certain extent. For that reason, when dealing with biodegradability internationally, materials with a biodegradability value of 60% or higher are expressed as "Readily biodegradable" through the OECD guideline technique. Based on the biodegradability data for each material according to the above criteria, 10 synthetic raw materials were selected as primary fragrance candidates, and are shown in Table 2 below.

flavor candidate cis-3-Hexenol Allyl heptanoate Nerolidol Hedione 3-Hexen-1-yl methyl carbonate Linalyl acetate Ethyl linalool Citronellyl acetate Sandalore Vanillin

[Example]

Example 1. Preparation of perfume composition with high biodegradability

It was prepared with the composition and content of Table 3 using the fragrance candidate selected in Preparation Example 1-3. Green, herbal, fruity, floral, and woody smells, which are highly preferred, to realize a natural herbal scent in line with the purpose of a highly biodegradable fragrance composition The fragrance ingredients with the red fragrance were selected mainly. Unless otherwise indicated in this specification, content is in weight percent.

Furtherance Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 cis-3-Hexenol 2.50 1.50 0.50 0.49 0.49 Allyl heptanoates 0.70 0.70 0.70 0.69 0.69 Nerolidol 2.00 1.00 1.00 0.98 0.98 Hedione 20.00 31.50 31.50 30.87 30.87 3-Hexen-1-yl methyl carbonate 0.30 0.25 0.25 0.24 0.24 Linalyl acetate 35.50 42.05 42.55 41.70 41.70 Ethyl linalool 30.00 16.50 16.50 16.17 16.17 Citronellyl acetate 5.00 2.00 2.00 1.96 1.96 Sandalore 1.00 2.00 2.50 2.45 2.45 Vanillin 3.00 2.50 2.50 2.45 2.45 Grapefruit oil - - - 0.50 1.00 geranium oil - - - 0.50 0.50 Clary sage oil - - - 1.00 0.50 Sum 100.00 100.00 100.00 100.00 100.00

Examples 2-3. Preparation of perfume composition with high biodegradability

Even if the biodegradability is high, preference is also an important factor to be considered for the functionality of the fragrance. In the case of the perfume composition prepared in Example 1, although it showed a generally positive preference with a natural-friendly feeling, there was an opinion that the fragrance did not blend smoothly and a specific fragrance stood out. Therefore, in order to solve this problem, a method to improve the palatability of the fragrance and the sense of naturalness/luxury was sought.

In order to reduce the chemical smell coming from synthetic raw materials and to round the fragrance composition smoothly, raw materials were screened among natural fragrances, and the key components of natural fragrance formulation were selected and redesigned to give a luxurious feeling while matching with Example 1. did About 2% of the key component of the natural fragrance composition was additionally used based on the total weight of the fragrance composition, and it was intended to preserve the natural feeling while maintaining the existing fragrance. Specifically, to add a refreshing herbal feel, grapefruit oil, a citrus type that gives a refreshing feeling, geranium oil, a fresh floral type, and clary sage, a rustic herbal type Examples 2 and 3 were prepared with the composition and content shown in Table 3, respectively, by selecting clary sage oil.

In the composition of Example 2, 1% of clary sage oil was applied to emphasize the feeling of herbs, but the unique rustic feeling was strong and dominant. In order to secure this, in the case of the composition of Example 3, the content of clary sage oil was reduced and the ratio of grapefruit oil was increased to improve the fresh fragrance from citrus peel.

[Comparative example]

Comparative Examples 1-2. Preparation of perfume composition

A perfume composition was prepared with the composition and content of Table 3 above.

As a result, in Comparative Examples 1 and 2, cis-3-Hexaneol and 3-hexen-1-yl methyl carbonate had a harsh green flavor.

[Experimental example]

Evaluation of Fragrance Satisfaction of Biodegradable Perfume Compositions

The fragrance satisfaction of the perfume composition was evaluated by checking whether or not a natural/eco-friendly feeling as a biodegradable perfume composition was obtained. Specifically, the fragrance compositions prepared in Comparative Examples 1 and 2 and Examples 1 and 3 were evaluated by a 5-point evaluation method according to Table 4, targeting 20 ordinary women aged 20-45 (average age: 31.4 years old). and the results are shown in Table 5.

score Does it feel natural/eco-friendly? 5 It feels very eco-friendly 4 I feel a little greener 3 so so 2 It feels a little chemical. One It feels very chemical.

number age gender Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 One 25 female One One 2 4 4 2 33 female One One One 3 5 3 31 female One One 2 4 5 4 31 female 2 2 3 3 4 5 29 female One One 2 4 5 6 27 female 2 2 2 3 5 7 45 female 2 2 2 3 5 8 28 female One 2 2 4 4 9 25 female 2 2 3 3 5 10 33 female One One 2 3 5 11 29 female One One One 4 4 12 38 female One 2 3 4 4 13 26 female 2 2 3 5 5 14 34 female One One 2 4 5 15 40 female One 2 2 4 4 16 29 female One One One 4 4 17 26 female One 2 2 3 5 18 20 female 2 2 3 4 5 19 36 female One One One 4 5 20 43 female One One 2 5 5 average 31.4 1.3 1.5 2.05 3.75 4.65

As a result, in the case of Comparative Examples 1 and 2 prepared only with synthetic fragrances, there were many opinions that they had a chemical feeling. Specifically, many of the opinions were that the synthetic raw materials did not harmonize and the fragrance of Hash Green was felt a lot.

On the other hand, in the case of Example 1, in which the green fragrance was reduced and the fragrance components of the warm flower and wood series were upwardly adjusted, it was felt relatively fresh and the opinion on the chemical feeling was low. However, there were still opinions that it seemed to come from synthetic fragrances and that certain chemical ingredients were splashing. On the other hand, in the case of Example 2 and Example 3 in which three natural flavors were selected and added, the response that natural/eco-friendly feeling increased. In particular, the composition of Example 3 with a high content of grapefruit oil among the three selected natural flavoring agents had a higher natural feeling score than the composition of Example 2 with a high content of clary sage oil. That is, the fragrance composition according to one aspect may induce an environmentally friendly fragrance by additionally including a natural fragrance in synthetic raw materials having high biodegradability.

Evaluation of fragrance preference of biodegradable perfume composition

In the same manner as above, the fragrance preference of the perfume composition was evaluated according to Table 6 below, and the results are shown in Table 7.

score preference 5 very good 4 a little good 3 so so 2 a bit not good One not very good

number age gender Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 One 25 female 3 3 4 4 5 2 33 female One 2 3 4 4 3 31 female 3 4 4 5 5 4 31 female 3 4 5 4 5 5 29 female 3 3 4 3 4 6 27 female 2 2 3 4 4 7 45 female One 2 2 3 5 8 28 female 3 3 4 4 4 9 25 female 4 4 4 4 5 10 33 female One 2 3 4 4 11 29 female 2 3 3 5 4 12 38 female 2 2 3 5 5 13 26 female 2 2 3 3 5 14 34 female 4 4 5 5 5 15 40 female One One 3 4 4 16 29 female 3 3 4 4 5 17 26 female 2 3 3 3 5 18 20 female 2 2 3 4 5 19 36 female 3 3 4 4 4 20 43 female 3 3 4 4 5 average 31.4 2.4 2.75 3.55 4 4.6

As a result, Comparative Examples 1 and 2, which were combined only with synthetic raw materials, showed very low satisfaction. Example 1, which relatively reduced the feeling of hash green and reinforced the soft floral scent, showed a positive preference. However, it did not lead to high preference due to the harsh chemical odor coming from synthetic raw materials.

On the other hand, in the case of Examples 2 and 3 including grapefruit oil, geranium oil, and/or clary sage oil, which are natural fragrances, it was confirmed that the preference increased as the natural feeling of the fragrance increased. In particular, in the case of Example 3 in which the content of grapefruit oil was increased, it was confirmed that the preference was the highest because it gave a more refreshing feeling.

Therefore, the perfume composition according to one aspect includes a synthetic perfume and a natural perfume component made of readily biodegradable, so as to have high biodegradability, induce a natural scent, and improve consumer preference and satisfaction.

The above description of the present invention is for illustrative purposes, and those skilled in the art can understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, the embodiments described above should be understood as illustrative in all respects and not limiting.

Claims (9)

A biodegradable perfume composition comprising cis-3-Hexenol, hedione and sandalore as active ingredients,
A perfume composition comprising 0.01 to 1.0% by weight of cis-3-hexenol, 25 to 35% by weight of Hedione and 2.0 to 5.0% by weight of Sandalore, based on the total weight of the composition. delete The method according to claim 1, grapefruit oil, geranium oil, clary sage oil, lemon oil, chamomile oil, eucalyptus oil, A fragrance composition further comprising at least one natural fragrance selected from the group consisting of lavender oil. The perfume composition according to claim 3, wherein the natural perfume is included in an amount of 0.1 to 3.0% by weight based on the total weight of the composition. The perfume composition according to claim 1, wherein the biodegradability is 60 to 100%. The method of claim 1, allyl heptanoate, nerolidol, 3-hexen-1-yl methyl carbonate, linalyl acetate, ethyl 1 selected from the group consisting of linalool, citronellyl acetate, vanillin, phenylethyl alcohol, terpineol, and ionone A perfume composition further comprising at least one synthetic perfume. A personal care product comprising the perfume composition of claim 1. The product of claim 7 , wherein the personal care product is selected from the group consisting of cosmetics, hair care products, toiletries, cosmeceuticals, beauty aids, insect repellents, personal care and cleansing products. A home care product comprising the perfume composition of claim 1.