JP2001064668A - Fragrance - Google Patents

Abstract

(57) [Summary] [Problem] To provide an unprecedented novel fragrance which maintains the initial scent for a long time when scent is applied to various articles. Furthermore, a fragrance that can leave a scent on the object to be cleaned even after washing, a fragrance composition containing the same,
A skin external preparation composition and a cleansing composition are provided. A flavoring agent comprising a hydrophobic group-containing polysaccharide derivative, more specifically, 0.1 to 1 per 100 monosaccharides of a polysaccharide.
A fragrance comprising a hydrophobic group-containing polysaccharide derivative into which 0 hydrophobic groups have been introduced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fragrance, a fragrance composition, an external preparation for skin and a cleansing composition.
More specifically, the present invention relates to a fragrance having excellent water resistance, comprising a hydrophobic group-containing polysaccharide derivative, and a fragrance composition, a skin external preparation composition and a cleansing composition containing the fragrance.

[0002]

2. Description of the Related Art Fragrances are aromatic products such as fragrances, colognes and perfumes, cosmetics such as creams, lotions and antiperspirants, hair care products such as rinses and conditioners, bath products, food products and the like, and washing for clothing. Agent, cleaning agent for human body,
It is also widely used in cleaning agents for homes and shampoos. In such fragrance-related fields, those conventionally used for the purpose of delaying the volatility of the whole compounded fragrance such as cosmetic fragrances and food fragrances for the purpose of maintaining the initial fragrance in a well-balanced manner in addition to fragrance purposes. there were. The compounded fragrance is composed of various kinds of fragrant components from those with high volatility to those with low volatility, but if left as it is, the more volatile fragrance components volatilize sooner, The balance of the incense tone will be lost and its value will be lost. In order to prevent such a state, a substance used as a fragrance is required in the fragrance and among the fragrance-related substances, and such fragrance has been studied in various ways. Hercoline, alkylene glycol,
Solvents such as alkyl citrate and benzyl benzoate, and fragrances such as peruvian balsam, vetiver benzoin, labdanum, oak moss and patchouli have been used.

Recently, Japanese Unexamined Utility Model Publication No. 6-16471 discloses a technique in which a scent is permanently diffused from an anodic oxide film in which a scent is sealed by semi-sealing. As described above, it is difficult to maintain the fragrance of the fragrance in a well-balanced manner as a technical problem, and has been a problem in various fields. In particular, many of the conventionally known fragrances have strong skin irritation, and it is necessary to use them while paying attention to irritation and the like. In addition, odorless fragrances that can delay the volatility of the entire blended fragrance and maintain the initial fragrance for a long time, and are familiar with other scented components and do not inhibit the fragrance, have been generally used until now. Was not known. In addition, when a fragrance is added to the cleaning agent, even if these fragrance-retaining fragrances and fragrance retention agents are used, the fragrances are solubilized by the action of the surfactant and are washed away. Even if a scent is felt during washing, almost no scent remains on the object to be washed after washing, that is, the palatability is improved until after washing, or masking of unpleasant odor of the object to be washed is performed. There is a problem that the effect of the fragrance, such as performing, cannot be fully utilized. On the other hand, as emulsions of oils and fats, hydrophobic group-containing polysaccharide derivatives have hitherto been known in the field of pharmaceuticals (JP-A-63-319046, JP-A-3-2946).
No. 92301), however, it has never been known that this is particularly effective as a fragrance.

[0004]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a novel fragrance which maintains the initial fragrance of various articles for a long time. A second object of the present invention is to provide a fragrance composition containing the fragrance. A third object of the present invention is to provide a skin external preparation composition. Still another object of the present invention is to provide a detergent composition that can leave a scent on an object to be cleaned even after cleaning.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above-mentioned problems, and as a result, have found that a hydrophobic group synthesized with a hydrophobic group having a high affinity for a hydrophobic surface and a polysaccharide as constituent units. The present inventors have found that a functional group-containing polysaccharide derivative is water-resistant and has excellent characteristics as a fragrance-preserving agent for maintaining the initial fragrance for a long time, and completed the present invention. That is, the present invention provides the following [1] to [8]. [1] A flavoring agent comprising a hydrophobic group-containing polysaccharide derivative. [2] A flavoring agent comprising a hydrophobic group-containing polysaccharide derivative obtained by introducing 0.1 to 10 hydrophobic groups per 100 polysaccharide monosaccharides. [3] A fragrance composition comprising the fragrance according to [1] or [2]. [4] The fragrance composition according to [3], which is for pets. [5] A skin external preparation composition containing the fragrance according to [1] or [2]. [6] The composition for external use on skin according to [5], which is for pets. [7] A detergent composition containing the fragrance according to [1] or [2]. [8] The cleaning composition according to [7], which is for pets.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is a fragrance comprising a polysaccharide derivative having a hydrophobic group. The hydrophobic group-containing polysaccharide derivative according to the present invention is generally regarded as a hydrophobic group-containing polysaccharide derivative, and refers to a hydrophobic group-containing polysaccharide derivative obtained by introducing a hydrophobic group into a polysaccharide. . Preferred as the hydrophobic group-containing polysaccharide derivative used in the present invention is a derivative obtained by using a polysaccharide as a raw material and reacting a part of the polysaccharide with a hydrophobic group. Examples of such a hydrophobic group-containing polysaccharide derivative include pullulan, amylose, xyloglucan, amylopectin, dextran, dextrin, cyclodextrin, mannan, hydroxyethyldextran, levan, inulin, chitin, chitosan, and water-soluble cellulose. To the saccharide via an appropriate molecule,
There are hydrophobic group-containing polysaccharide derivatives obtained by chemically bonding hydrophobic groups, and these can be preferably used in the present invention from the viewpoint of availability.

[0007] For example, siliconized polysaccharides used in JP-A-10-29910 and JP-A-10-18
Pullulan fatty acid ester used in JP-A-2341 and JP-A-53-142540;
Dextran fatty acid ester used in JP-A No. 107-107, JP-A-2-144140 and JP-A-6-144140.
Polysaccharide-sterol derivatives disclosed in JP-A-3-319046 and JP-A-3-292301 can be preferably used as a kind of the hydrophobic group-containing polysaccharide derivative according to the present invention. Among these, the polysaccharide-sterol derivative is a hydrophobic group-containing polysaccharide derivative having good performance such as water resistance, and further, the pullulan-sterol derivative in which the polysaccharide portion is pullulan has the best performance. Among these, polysaccharide 100
A hydrophobic group-containing polysaccharide derivative obtained by introducing 0.1 to 10 hydrophobic groups per monosaccharide is more preferably used as a flavoring agent. At this time, the number of introduced hydrophobic groups is 10
If the number is less than 0.1 per 0 monosaccharide, it is easy to peel off from the surface of the hydrophobic substrate, and the duration of the fragrance retention effect is short. If the number is more than 10, the fragrance retention of the polysaccharide is reduced by the hydrophobic group. Since the fragrance retention effect may be weakened, the amount of the introduced hydrophobic group is preferably adjusted in an appropriate range of about 0.1 to 10 per 100 monosaccharides of the polysaccharide.

[0008] The method for producing the hydrophobic group-containing polysaccharide derivative used in the present invention may be synthesized by appropriately devising based on known chemical knowledge in order to obtain the desired hydrophobic group-containing polysaccharide derivative. Alternatively, it may be synthesized by referring to known publications that disclose a method for producing a hydrophobic group-containing polysaccharide derivative. For example, as a hydrophobic group-containing polysaccharide derivative, polysaccharide-
When a sterol derivative or the like is used, see JP-A-3-292.
Production by the method described in Japanese Patent Publication No. 301,
It is preferably performed. More preferably, from the viewpoint of the effect as a flavoring agent and the like, 0.1 to 10 hydroxyl groups per 100 sugar units constituting the polysaccharide are represented by the following general formula (1)

[0009]

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The hydrophobic group-containing polysaccharide derivative substituted with the group represented by the formula (1) has high environmental degradability and high biosafety, and is therefore suitably used as a fragrance for clothes and hair. At this time, R ¹ is a hydrocarbon group having 1 to 50 carbon atoms.
It may be cyclic and may be saturated or unsaturated, but is preferably a straight-chain saturated hydrocarbon group having 3 to 8 carbon atoms. R ² has 1 carbon atom
2 to 50 hydrocarbon or sterol groups, preferably sterol residues. For example, a cholesterol residue, a stigmasterol residue, a β-sitosterol residue, a lanosterol residue, and an ergosterol residue are preferable. From the viewpoint of availability, a cholesterol residue is most preferred. Such a hydrophobic group-containing polysaccharide derivative can be synthesized by using a compound having a hydrophobic group at one end of a molecule and an isocyanate group at the other end, and reacting with a hydroxyl group of the polysaccharide. A compound having a hydrophobic group at one end of a molecule and an isocyanate group at the other end can be obtained, for example, by the following reaction formula (2)

[0011]

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As shown in the above, the isocyanate group at one end of the diisocyanate compound is reacted with a hydroxyl group of a hydroxyl group-containing hydrocarbon or a sterol having 12 to 50 carbon atoms, for example, by a urethane bond. Obtained by combining. At this time, as the hydroxyl group-containing hydrocarbon molecule having 12 to 50 carbon atoms used in the reaction with the diisocyanate compound, any known hydrocarbon having 12 to 50 carbon atoms having at least one hydroxyl group may be used. For example, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol,
Hydroxy group-containing hydrocarbons derived from alcohols such as araquinyl alcohol, docosanol, pentacosanol, hexacosanol, and octacosanol are preferred. As the sterol, for example, cholesterol, stigmasterol, β-sitosterol, lanosterol, ergosterol and the like are used, and cholesterol is preferred from the viewpoint of availability. The diisocyanate compound to be reacted with sterol is OCN-R ^1-
A compound represented by NCO and in which R ¹ is a hydrocarbon group having 1 to 50 carbon atoms is preferable, for example, ethylene diisocyanate in which R ¹ is an ethylene group, butylene diisocyanate in a butylene group, hexamethylene diisocyanate in a hexamethylene group, And diphenylmethane diisocyanate which is a diphenylmethane group. Of these, butylene diisocyanate and hexamethylene diisocyanate are particularly preferably used. The polysaccharide-sterol derivative preferably used in the present invention can be obtained by reacting the above-described compound having a hydrophobic group at one end of a molecule and an isocyanate group at the other end with a polysaccharide. The reaction of a compound having a hydrophobic group at one end of a molecule and an isocyanate group at the other end with a polysaccharide is performed by, for example, the following reaction formula (3)

[0013]

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As shown in the above, the reaction is carried out by a one-step addition reaction between a hydroxyl group of a monosaccharide constituting a polysaccharide and an isocyanate group of a compound having a hydrophobic group at one end of a molecule and an isocyanate group at the other end. be able to. In the reaction formula (3),
Although a reaction between one hexasaccharide unit and a compound having an isocyanate group is shown as a model, in the synthesis of the hydrophobic group-containing polysaccharide derivative used in the present invention, the sugar unit constituting the polysaccharide is used. 0.1 ~ per 100
It is preferable to cause a reaction as shown in the reaction formula (3) for ten hydroxyl groups from the viewpoint of enhancing the effect as a fragrance. As the raw material polysaccharide used in the above reaction, any polysaccharide can be used, and in particular, pullulan, amylose, xyloglucan, amylopectin, dextran, dextrin, cyclodextrin, mannan, hydroxyethyldextran , Levan, inulin, chitin, chitosan, water-soluble cellulose and the like are preferably used. These polysaccharides may be of natural or synthetic origin, and may be of any molecular weight as long as they are available, but more effective when used as a flavoring agent. In order to demonstrate, an average molecular weight of 100
It is preferably about 0 to 1,000,000. As the kind of the polysaccharide, any polysaccharide can be usually used, but pullulan is particularly preferably used from the viewpoint of the effect when blended as a flavoring agent.

When a polysaccharide is reacted with an isocyanate group of a compound having a hydrophobic group at one end of the molecule and an isocyanate group at the other end of the molecule, a solvent having a hydrophobic group at one end of the molecule is used. A solvent in which both the compound having an isocyanate group at the other end and the polysaccharide are dissolved, and a solvent in which the hydrophobic group-containing polysaccharide derivative as a reaction product is dissolved is preferable.Typically, dimethylformamide, dimethylsulfoxide, formamide, dioxane, An aprotic solvent such as tetrahydrofuran is preferably used. The reaction temperature and time at this time are appropriately selected according to the progress of the reaction, depending on the polysaccharide and the solvent used, but the reaction is preferably performed at 0 to 200 ° C. for about 1 to 48 hours.

The charging ratio between the polysaccharide and the compound having a hydrophobic group at one end of the molecule and an isocyanate group at the other end may be any ratio, and by changing the charging ratio, the hydrophobic group to the polysaccharide is changed. Can be appropriately controlled, but 0.1 per 100 saccharide units constituting the polysaccharide.
When 10 to 10 hydrophobic groups are introduced, 10
It is desirable that the amount be in the range of 0.1 to 500 mol equivalent relative to 0 monosaccharide unit. As a method for purifying the hydrophobic group-containing polysaccharide derivative thus obtained, a reprecipitation purification method, a separation / purification method by various types of chromatography, a dialysis method, and the like can be used. As a drying method, a freeze drying method or a vacuum drying method is desirable.

As described above, among the thus produced hydrophobic group-containing polysaccharide derivatives, from the viewpoints of safety, ease of production, performance, etc., the average molecular weight is 1,000 to 1,000,000.
To the degree of pullulan, 0.1 ~ per 100 pullulan monosaccharides
A pullulan-cholesterol derivative obtained by reacting a compound having a sterol group at one end of a molecule and an isocyanate group at the other end so that sterol groups are introduced at a ratio of 10 is the most excellent, It is suitably used as an agent.

When the fragrance of the present invention is used, it is usually sufficient that the fragrance of the present invention and a conventionally known fragrance are finally used under the coexisting condition. Further, the fragrance of the present invention and a known fragrance may be blended to form an appropriate shape and used as a fragrance. In addition, as a well-known fragrance, a fragrance-retaining fragrance generally known to have a fragrance-retaining property (here, it has a fragrance-retaining property itself, or when it is blended with another fragrance, it may be used as another fragrance) On the other hand, a fragrance as if it acts as a fragrance may be used as a fragrance and mixed with the fragrance of the present invention to form a fragrance composition. As the known fragrance that can be blended with the fragrance of the present invention, any conventionally known fragrance can be used without any limitation. For example, a natural fragrance, a synthetic fragrance, a fragrance-preserving fragrance and the like are preferably exemplified. it can.

For example, well-known natural fragrances include ylang-ylang oil, lavender oil, rose oil, jasmine oil, clary sage oil, sandalwood oil, elemi oil, patchouli oil, Peruvian balsam oil, and trubal sam oil.

Examples of synthetic flavors include cis-3-hexenol, hexylcinnamic aldehyde, cinnamic alcohol, vanillin, coumarin, limonene, gamma-undecalactone, 6-acetyl-1,1,3,3.
4,4,6-hexamethyl-tetrahydronaphthalene,
5-acetyl-1,1,2,3,3,6-hexamethylindane, cyclogentadecanone, phenylethyl alcohol, amylcinnamic aldehyde, rose oxide, heliotropin and the like.

Examples of the fragrance-retaining fragrance include essential oils, balsams, gums, ole oranges, animal extracts, fragrance-retaining synthetic fragrances, and almost odorless synthetic fragrances. Here, the essential oils include basil, nutmeg, boad rose, origum, cananga, patchouli, cassia,
Peru, Cedarwood, Saffron, Clove, Sandalwood, Coriander, Sassafras, Cumin, Cypress, Tarragon, Guayawood, Iris, Linaloe, Valerian, Mace, Vetiver, Clary Sage, Angelica, Ampud and the like. As balsam, gum, and ole oranges, moss, oak moss, benzoin,
Olivenum, chamomile, oppoponax, cascarilla,
Love Dunham, Sandals, Elemi, True, Galvanham,
Toncarbin, geranium, vanilla, ginger, vetiver, iris, juniper and the like. Animal extracts include ambergris, musk, civet, castorium and the like.

Examples of the fragrance-retaining synthetic fragrance include acetylisoeugenol, amylbenzoate, amylphenylacetate, amylsalicylate, benzophenone, benzylcinnamate, benzylformate, benzylisoeugenol, benzylphenylacetate, benzylpropionate and benzylvaleria. Nate, benzylideneacetone, butylphthalate, cinnamic acid,
Cinnamamic alcohol, cinnamaldehyde, cinnamyl acetate, cinnamyl cinnamate, coumarin, paracresyl acetate, cuminaldehyde, dimethylbenzylcarbinol, diphenylmethane, diphenyloxide, ethyl anthranilate, ethyl cinnamate, ethyl phenyl acetate, Ethyl salicylate, methyl eugenol, naphthyl butyl ether,
Phenylacetic acid, santalol, skatole, vanillin,
Indole, musk ketone, exaltolide, hydroxycitronellal, exaltone, cyclamenaldehyde, phenoxyethanol and the like.

Almost odorless synthetic fragrances include amylphthalate, benzoic acid, cyclohexanol oxalate, diethylene glycol, ethyl phthalate, resorcinol acetate, triethylene glycol, malonic esters, succinic esters, adipine Acid esters, sebacic esters, tartaric esters, citrate esters, myristic acid, stearic acid and the like.

These natural fragrances, synthetic fragrances or fragrance-retaining fragrances may be used alone as a fragrance-preserving composition by blending them individually with the fragrance-preserving agent of the present invention. You may mix | blend as a fragrance | flavor and use it as a fragrance | flavor composition. In that case, the amount of the flavoring agent of the present invention may be freely selected as long as the performance of the present invention is not hindered. It may be blended in an amount of 99% by weight, and is more preferably blended in an amount of 5 to 90% by weight from the viewpoint of maintaining the fragrance retention property and the blending property. At this time, if it is less than 1% by weight, it is not preferable because the fragrance retention is hard to be maintained, and if it is more than 99% by weight, it is not preferable from the viewpoint of mixability. The amount of the fragrance varies depending on the purpose and the components of the fragrance.
001% by weight to 10% by weight.

Further, the fragrance composition of the present invention contains the above-mentioned fragrance and a fragrance. If necessary, further additives may be added. As the additives, any additives can be used freely as long as they are blended in the fragrance composition without any problem. For example, organic acids, inorganic salts, enzymes, and hot spring ingredients can be used. Requires surfactants, alcohols, sugars, vitamins, amino acids, antioxidants, preservatives, herbs, crude drugs, pigments, bases, humectants, stabilizers, thickeners, masking agents, solvents, etc. It can be blended accordingly.

Among these, benzoic acid, succinic acid, malic acid, fumaric acid, tartaric acid, citric acid, pyrrolidone carboxylic acid and the like are used as organic acids. The inorganic salts are not particularly limited, but include sodium sulfate, magnesium sulfate, sodium hydrogen carbonate, sodium carbonate, sodium sesquicarbonate, sodium chloride, ammonium chloride, sodium nitrate, potassium nitrate, calcium nitrate, sodium polyphosphate, sodium phosphate, and iron sulfate. Sodium phosphate, calcium oxide, calcium carbonate, magnesium oxide, aluminum sulfate, sodium thiosulfate, magnesium carbonate, potassium chloride, potassium sulfide, alum, metasilicic acid, silicic anhydride, and the like are used. The enzyme is not particularly limited, but pancreatin, pepsin, trypsin, chymotrypsin, cathepsin, papain, promelain, ficin and the like are used. The surfactant is not particularly limited, but includes lecithin, sucrose fatty acid ester, polyoxyethylene hydrogenated castor oil, isopropyl myristate, glycerin fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, tetraolein Acid polyoxyethylene sorbite,
Polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyethylene glycol fatty acid ester, polyglycerin fatty acid ester, sodium α-olefin sulfonate, sodium lauryl sulfate, cetyl sulfate, sodium polyoxyethylene lauryl sulfate, lauryl sulfosuccinate Disodium, carboxybetaines, aminocarboxylic acids, sulfobetaines and the like are used. The alcohol is not particularly limited, but lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, cholesterol, 2-hexyldecanol and the like are used. The saccharide is not particularly limited, but hyaluronic acid, chondroitin, chondroitin sulfate, chitin, mannan, trehalose, lactose and the like are used.

The vitamins are not particularly limited, but include sodium flavin adenine dinucleotide, cyanocobalamin, retinol, pyridoxine hydrochloride, pantothenic acids, tocopherol acetate, vitamin A, vitamin B, vitamin C, vitamin D, vitamin E, vitamin F. , Vitamin K, vitamin P, vitamin U, carnitine, ferulic acid, γ-oryzanol and derivatives thereof. As amino acids, glycine, alanine,
Valine, leucine, isoleucine, serine, threonine, phenylalanine, tyrosine, tryptophan, cysteine, methionine, proline, hydroxyproline, aspartic acid, glutamic acid, arginine, histidine, lysine, aminoethylsulfonic acid and the like are used. The antioxidant is not particularly limited, but propyl gallate, ascorbic acid, ascorbic acid palmitate, ascorbic acid stearate and the like are used.
The herbs or herbal medicines are not particularly limited, but may include goshyu, sojutsu, zakutsutsu, valerian, liquorice, keikai, kouboku, senkyu, touki, spruce, ginger, ogon, sanshishi, kaiyou, aloe, carrot, keihi, peony, peppermint leaf, Bakuryo, Dokukatsu, Shobu, Matsubusa, Juniper, Juyaku, Ryuno, Saffron, Oubak, Fennel, Chimpi, Campi, Chamomile, Melissa, Radish,
Willows, camphor trees, elderberry, sedges, naginata koji, yuzu, daidai, peach, honey bee, loquat, honeysuckle, yorigusa, bodaiju, horse chestnut, yarrow, hops, rosemary, lavender, birch, kissin, malonie, alnica, etc. Used.

The pigments also do not interfere with the object of the present invention.
Any dye can be used, but usually, synthetic dyes of Blue No. 1, Blue No. 2, Yellow No. 4, Yellow No. 5, Yellow 202, Red No. 106, and Orange No. 205 are used. From the viewpoint of enhancing the natural image of the product, natural dyes are preferably used.Specifically, caramel dyes, annatto dyes, paprika dyes, cochineal dyes,
Monascus pigment, gardenia pigment, safflower pigment, red radish pigment, red cabbage pigment, beet red, berry pigment, red diso pigment, purple potato pigment, spirulina pigment, chlorophyll, squid pigment, cacao pigment, marigold pigment, extracted carotene, etc. Can be preferably used, and can be used in an appropriate amount as long as the object of the present invention is not hindered. Examples of the base include, but are not limited to, white petrolatum, stearic acid, oleic acid, stearyl alcohol, cetanol, liquid paraffin, squalane, squalene, beeswax, and the like. Although it does not specifically limit as a humectant, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerin, diglycerin , Polyglycerin, sorbitol, mannitol, xylitol, maltitol, sodium hyaluronate, sodium chondroitin sulfate, sodium pyrrolidonecarboxylate, sodium lactate, collagen, elastin, mucin, phospholipids, ceramide, urea, trehalose, trehalose derivatives and the like. .

Examples of the stabilizer include, but are not limited to, ethylenediaminetetraacetate, citric acid, sodium sulfite, and sodium bisulfite. Examples of the thickener include, but are not particularly limited to, gum arabic, guar gum, carrageenan, polyvinylpyrrolidone, carboxyvinyl polymer, polyvinyl alcohol, methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, polyethylene glycol, hyaluronic acid, and polymers such as chondroitin sulfate. And the like. Examples of the masking agent include, but are not limited to, fennel oil, eucalyptus oil, cassia oil, peppermint oil, eugenol, prunes, herbs, and the like. Although it does not specifically limit as a solvent, water, ethanol, methanol, chloroform, acetone, dimethyl sulfoxide,
Examples include tetrahydrofuran, hexane, benzene, petroleum ether, lacquers, and thinners.

The fragrance composition contains the above-mentioned fragrance, perfume and other additives as necessary. The other additives used in this case are selected according to the intended purpose and shape. The above-mentioned additives are arbitrarily selected in any kind and amount, and are appropriately blended by a generally known method. Thereafter, the shape of the fragrance composition is powdered by a general fragrance composition manufacturing method. , Granules, tablets, solutions and the like. At this time, the fragrance composition from the viewpoint of ease of handling, granular,
Processing into a powder or a solution is preferably performed. The fragrance composition of the present invention can be used for flavoring various products. For example, fragrances, fragrance products such as perfume, bath products and toiletries such as deodorant fragrances, use of food such as outer skin of citrus fruits, decorative boxes, wrapping paper, dust paper,
In addition to paper products such as origami, it is used for hair care products such as rinses, conditioners, hair mousses, and hair colors. Or ink for ballpoint pens, paints, paints,
It can also be used by blending it with crayons. Further, it can be applied to a surface of metal, stone, glass, or the like, and can be used, for example, for jewelry or pendants. As described above, by using the fragrance composition of the present invention, the scent of various products can be controlled, and the product can be widely used as a scented product. As a target, in addition to the human body, it can be suitably used for livestock, pets, and the like. Targets for livestock include horses, cows, pigs, donkeys, sheep, chickens and the like. For pets, dogs, cats, monkeys, mice,
Guinea pigs, squirrels, small birds, weasels, raccoons, skunks and the like can be mentioned. The fragrance composition can also be applied to the surface of a base material of articles such as plastics, leather goods, rubber and fibers, or kneaded into these materials. When used by applying to the surface of a substrate, the application method may be an existing method such as a brush coating method, a roll coating method, a bar coater method, a spray method, a spin coating method, or a dip coating method. it can. When performing the coating, it is preferable to apply the flavoring composition of the present invention in a liquid state. In this case, when it is necessary to use a solvent, for example, methanol, ethanol, propanol, isopropanol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, water, methylene chloride, chloroform and a mixed solvent thereof are used. good. Of these solvents, alcohol solvents are particularly preferred. After the application of the fragrance composition-containing solution, a fragrance-preventing film can be formed on the substrate surface of the article by drying such as natural drying or forced drying. In addition, when the fragrance composition of the present invention is used by kneading it into a raw material such as plastic, for example,
As a plastic raw material, a polyacrylate, polycarbonate, polyvinyl chloride, polyethylene or the like is used, and a continuous production method can be preferably produced by an extrusion method or a continuous casting method. At this time, the amount of the flavoring agent composition in the raw materials may be appropriately adjusted. In this manner, a plastic plate into which the fragrance composition of the present invention has been kneaded can be easily produced. In addition to the uses of the fragrance composition described above, as a more preferred use of the fragrance composition of the present invention, the above-mentioned fragrance composition is further added with the additives mentioned later, especially for external use on the skin. It can be suitably used as an agent composition or a detergent composition.

The composition for external application to skin of the present invention can be used as a composition for external application to skin by blending it with the above-mentioned fragrance, fragrance, oily component and the like. The amount of the flavoring agent of the present invention contained in the skin external preparation composition may be an appropriate amount, and it is usually 0.01 to 40 per 100% by weight of the skin external preparation composition. It is preferably contained in the range of weight%. More preferably, it is in the range of 0.1 to 10% by weight. The oily component that can be used in the skin external preparation composition of the present invention is not particularly limited as long as it is an oily component that is usually used in a skin external preparation.
Examples include waxes, higher fatty acids, hydrocarbons, higher alcohols, esters, essential oils, and silicones. Here, as fats and oils, soybean oil, bran oil, jojoba oil, avocado oil, peppermint oil, hinoki oil, orange peel oil, almond oil,
Olive oil, cacao oil, sesame oil, persic oil, castor oil, coconut oil, mink oil, tallow, lard, fennel oil, eucalyptus oil, cassia oil, spearmint oil, linseed oil, fish oil, liver oil, vitamin A oil, tuna oil, mackerel oil Oils, saury oil, sardine oil, cod oil, herring oil, natural oils and fats such as lamprey oil and hardened oils obtained by hydrogenating these natural oils and fats, and synthetic glycerides such as myristic glyceride and 2-ethylhexanoic acid glyceride; And diglyceride. Some of the fats and oils belonging to the above fragrances are also mentioned. Examples of waxes include carnauba wax, whale wax, beeswax, and lanolin. Examples of the higher fatty acids include lauric acid, myristic acid, palmitic acid, pentadecanoic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, lanolinic acid, isostearic acid, eicosapentaenoic acid, and docosahexaenoic acid. The hydrocarbons include liquid paraffin, vaseline, paraffin, microcrystalline wax,
Ceresin, squalene, pristane, etc. Also,
Higher alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, cholesterol, 2-hexyldecanol, octacosanol and the like. Further, as esters,
Cetyl octanoate, myristyl lactate, cetyl lactate, myristyl myristate, isopropyl palmitate, isopropyl adipate, butyl stearate, decyl oleate, cholesterol isostearate and the like.

These oily components may be used in the skin external preparation composition in any amount, but are usually contained in the range of 3 to 40% by weight in 100% by weight of the skin external preparation composition. Is preferred. Further, the skin external preparation composition of the present invention may further contain additives as necessary.
The additives used may be any additives usually used in external preparations for skin, such as base materials, surfactants, fats and oils, humectants, stabilizers, preservatives, dyes, fragrances, bactericides, anti-inflammatory agents, and the like. Of the additives exemplified as the additives to be added to the fragrance composition, the additives generally used in external preparations for skin may be selected and used, and the amount may be appropriately selected. Good. The skin external preparation composition can be produced by homogenizing the raw materials by a known method using an emulsifier or the like. The dosage form of the external composition for skin can be cream, emulsion, spray, gel, paste, powder, solid or the like. These skin external preparation compositions can be preferably used as cosmetics such as creams, colognes, lotions, antiperspirants, and the like, and pharmaceutical preparations such as ointments and emulsions. As a target, in addition to the above-mentioned human body, it can be suitably used for livestock or pets.

The detergent composition of the present invention comprises the above-mentioned perfume preservative,
A fragrance and a surfactant may be blended and used as a cleaning composition. The surfactant used in the detergent composition is not particularly limited as long as it is a surfactant blended as a cleaning active ingredient. For example, nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants and the like can be preferably used. As the nonionic surfactant, fatty acid amide, polyoxyethylene alkyl ether, sugar ester, sugar ether,
Sugar amides and the like, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene monoacylate, sorbitan monoacylate, polyoxyethylene sorbitan monoacylate, glycerol monoacylate, polyoxyethylene alkylamine , Polyoxyethylene-polyoxypropylene random copolymer, polyoxyethylene-block copolymer and the like can be preferably used. Examples of commercially available nonionic surfactants include, for example, Nonion (trade name), manufactured by NOF Corporation, Monogly (trade name),
Nippon Oils and Fats Co., Ltd., Unigri Co., Ltd., Nippon Oils and Fats Co., Ltd., Starhome Co., Ltd., Nippon Oils and Fats Co., Ltd., Nymein. ｝, Pronon ｛brand name, manufactured by NOF Corporation, Dispanol ｛brand name, manufactured by NOF Corporation etc. can be preferably used.

As the cationic surfactant, a long-chain alkylamine acetate, a long-chain alkyltrimethylammonium chloride and the like can be preferably used. As a commercially available cationic surfactant, a cation (trade name, manufactured by NOF Corporation) can be preferably used.

Examples of the anionic surfactant include a carboxylic acid type anionic surfactant, a sulfate type anionic surfactant, and a sulfonic acid type anionic surfactant. As the carboxylic acid-based anionic surfactant,
Examples include higher fatty acid salts, N-acyl sarcosine salts, alkyl ether acetates, and polyoxyethylene alkyl ether acetates. Among them, as higher fatty acid salts,
For example, a base salt of a fatty acid having 8 to 22 carbon atoms may be mentioned.
Specific examples include base salts of single fatty acids such as lauric acid, myristic acid, palmitic acid, isostearic acid, and oleic acid, as well as mixed fatty acids such as coconut oil fatty acids and tallow fatty acids. Here, examples of the salt include inorganic basic salts such as sodium and potassium; ammonium salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, 2-amino-2-methylpropanol, 2-amino-2-methylpropanediol. Alkanolamine salts; basic amino acid salts such as lysine and arginine; Examples of commercially available anionic surfactants include, for example, Nonsalle (trade name), Nippon Oil & Fats Co., Ltd.
Brand name, Nilube brand name, Nippon Yushi Co., Ltd., Suncall® brand name, Nippon Yushi Co., Ltd. brand, Sun Alpha ™ brand name, Nippon Yushi Co., Ltd. brand, Marcel II Brand name, Nippon Yushi Co., Ltd., Lapisol®, brand name, Nippon Yushi Co., Ltd., Parsoft®, brand name, Nippon Yushi Co., Ltd., Sintrexus, brand name, Nippon Yushi ( Co., Ltd., Diapon Co., Ltd., Nippon Yushi Co., Ltd., Newrex Co., Ltd., Nippon Yushi Co., Ltd., Succinide, Co., Ltd., Nippon Yushi Co., Ltd.,
Trucks ｛brand name, manufactured by NOF Corporation, Polystar ｛brand name, manufactured by NOF Corporation, Sanamide ｛brand name, manufactured by NOF Corporation, fillet ｛brand name, NOF And Sunbase (trade name, manufactured by NOF Corporation) and the like can be preferably used.

Examples of the sulfonic acid type or sulfuric acid type anionic surfactant include sulfosuccinic acid type, isethionate type, taurate type, alkylbenzenesulfonic acid type, olefinsulfonic acid type, alkanesulfonic acid type, alkyl or alkenyl sulfate type and the like. Anionic surfactants are included. Here, examples of the sulfosuccinic anionic surfactant include sulfosuccinates of higher alcohols or ethoxylates thereof, sulfosuccinates derived from higher fatty acid amides, and salts thereof. Examples of the alkylbenzenesulfonic acid-based anionic surfactant include a linear or branched alkylbenzenesulfonic acid salt having an alkyl group having an average of 10 to 16 carbon atoms; Olefin sulfonates having 10 to 20 carbon atoms in one molecule; alkane sulfonates having an average of 10 to 20 carbon atoms in one molecule as alkanesulfonic acid-based anionic surfactants; An alkyl or alkenyl sulfate-based anionic surfactant having a linear or branched alkyl or alkenyl group having an average of 10 to 20 carbon atoms, and having an average of 0.1 or less per molecule.
5-8 moles of ethylene oxide, propylene oxide,
Butylene oxide, ethylene oxide and propylene oxide in a ratio of 0.1 / 9.9 to 9.9 / 0.1, or ethylene oxide and butylene oxide in a ratio of 0.1 / 9.
Examples thereof include an alkyl or alkenyl ether sulfate added at a ratio of 9 to 9.9 / 0.1 and an alkyl or alkenyl sulfate having an alkyl or alkenyl group having an average of 10 to 20 carbon atoms.

Examples of the amphoteric surfactant include imidazoline-based and betaine-based surfactants, and dimethylalkylbetaine is preferably used. As commercially available amphoteric surfactants, for example, Nissan Anone (trade name, manufactured by NOF Corporation) can be preferably used. These surfactants may be added alone or as a mixture.
The amount of the surfactant may be appropriately selected, but is preferably 1 to 50% by weight, particularly preferably 5 to 30% by weight in the detergent composition.

When the fragrance or the fragrance composition of the present invention is used for cleaning, the fragrance or the fragrance composition of the present invention is finally added to the cleaning system. As long as the activator and the object to be cleaned are present, as described above, the composition is blended as a detergent composition containing a fragrance, a fragrance, and a surfactant, and then added to the object to be cleaned and the cleaning system. More preferably, it is used.

The detergent composition of the present invention comprises a fragrance, a fragrance,
The content is 0.03 to 5% by weight, more preferably 0.3 to 1% by weight, in the system where the surfactant and the object to be cleaned are present. In particular, it is preferable to add the fragrance and the fragrance so as to be equal in weight.

The amount of the above-mentioned fragrance in the detergent composition is as follows:
It can be appropriately selected according to the purpose, such as imparting a strong scent or making it slightly fragrant, and varies depending on the type of fragrance, but is usually 0.01 to 5% by weight, particularly 0.1 to 1% by weight. Is preferred.

Further, in the cleaning composition of the present invention, as a further additive, a component usually used for a cleaning agent can be optionally used in combination within a range not to impair the effects of the present invention. For example, humectants such as propylene glycol, sorbitol, glycerin, etc., viscosity modifiers such as carboxyvinyl polymer, methylcellulose, ethanol, polyoxyethylene glycol distearate, pearling agents, pigments, ultraviolet absorbers, antioxidants, bactericides , A preservative and the like. In addition, among those exemplified as the additives to be added to the above-mentioned perfume preservative composition, an additive generally used in a detergent composition may be selected and added, and the amount may be appropriately selected. .

The cleaning composition of the present invention is not particularly limited as long as it requires a residual scent on the object to be cleaned, and is used for clothing, human body, hair, house, floor or livestock. It is useful as a cleaning agent for pets and pets. As a target, in addition to the above-mentioned human body, it can be suitably used for livestock or pets with strong animal odor. Specific examples of livestock and pets as the object include those described above. Further, the cleaning composition of the present invention is produced by a conventional method, and can be in the form of a paste, gel, liquid, or solid. A particularly preferred usage is to use it as a detergent such as a detergent for clothes, a detergent for humans, a detergent for houses and the like. It is particularly preferable to use as a body shampoo and a hair shampoo as a human body cleaner.

[0043]

The perfume preservative of the present invention is excellent in perfume preservation effect and maintains the initial perfume for a long time. Further, the detergent composition containing the fragrance of the present invention does not wash off the fragrance and the fragrance of the object to be cleaned even after washing and rinsing. It has an excellent effect of suppressing volatilization of odor and enhancing the fragrance retention after drying. In addition, the skin external preparation composition of the present invention has an effect of maintaining a fragrance for a long time by using a hydrophobic group-containing polysaccharide derivative. Furthermore, the cleaning composition of the present invention not only maintains the fragrance for a long time by using the hydrophobic group-containing polysaccharide derivative, but also imparts a fragrance to the object to be cleaned and maintains the fragrance retention after drying. effective.

[0044]

The present invention will be described in detail with reference to the following examples. Next, test methods and the like will be described. Reference Example 1 <Synthesis of N- (6-isocyanatohexyl) cholesteryl carbamate> In a 1-L eggplant-shaped flask, 25 g (0.065 mol) of cholesterol and 300 m of toluene were placed.
L and dissolve, then add 17 mL of triethylamine.
(0.12 mol) was added. There, toluene 300
Hexamethylene diisocyanate 161 dissolved in mL
g (0.96 mol), and reacted at 80 ° C. for about 6 hours under a nitrogen atmosphere. After the reaction was completed, toluene and excess hexamethylene diisocyanate were removed under reduced pressure. The resulting yellow oily residue was allowed to stand at room temperature overnight to produce pale yellow crystals. The crystals were taken out, about 1 liter of hexane was added, the mixture was shaken vigorously, and the supernatant was removed by decantation. After performing this washing operation four times in total, the solid was dried under reduced pressure at room temperature for 3 hours to obtain a white solid. The yield is 18.25 g and the yield is 50.
9%. The results of IR measurement of the obtained product are shown. IR (KBr, cm ^-1 ): 3260, 2320, ¹
680, 1130. From the above, it was confirmed that N- (6-isocyanatohexyl) cholesteryl carbamate was obtained.

Synthesis Example 1 <Pullulan-cholesterol derivative (hereinafter CH) into which 0.9 cholesteryl groups are introduced per 100 pullulan monosaccharides
Synthesis of P0.9) 40 g of pullulan (average molecular weight, 108000) and 420 mL of dimethyl sulfoxide were added to an eggplant-shaped flask of> 1 L, and stirred and dissolved at 80 ° C. under a nitrogen atmosphere. There, N-synthesized in Reference Example 1
1.78 g (3.21 mmol) of (6-isocyanatohexyl) cholesteryl carbamate was added to pyridine.
The solution dissolved in 4 ml (0.40 mol) was added, and 90
The reaction was carried out at 1.5 ° C. for 1.5 hours. After completion of the reaction, dimethyl sulfoxide was removed under reduced pressure, and the obtained oily residue was dropped into 6 L of acetone to form a precipitate. After removing the supernatant, 4 L of acetone was added to the obtained precipitate, and the mixture was left overnight at room temperature. The precipitate was collected by filtration and dried under reduced pressure. The obtained solid was dissolved in dimethyl sulfoxide, and this was filled in a dialysis membrane (Spectropore, Spectra / Por3, molecular weight cut off: 3500), and dialyzed against distilled water for one week. A white solid was obtained by freeze-drying 1.5 L of the obtained polymer solution by an ordinary method. Yield 3
1.7 g (76.2% yield). Next, the product ¹ H-NM
The measurement results of R and IR are shown. ¹ H-NMR ((δpp
m), DMSO-d6 / D2O = 20/1, vol, TM
S): 0.68-2.40, 2.60-4.60, 4.
60-5.05. IR (KBr, cm ^-1 ): 1680,
1180-900. From the ¹ H-NMR spectrum, the peak area derived from a cholesterol group (δ = 0.6 to 2.
3) and the peak area derived from pullulan (δ = 4.7-5.
From 1), the degree of substitution of cholesterol groups per 100 monosaccharides was calculated. As a result, the degree of substitution of cholesterol groups per 100 monosaccharides was 0.9. From the above data, it was confirmed that the obtained compound was CHP0.9.

Synthesis Example 2 <Pullulan-cholesterol derivative (hereinafter CH) having 0.1 cholesteryl groups introduced per 100 pullulan monosaccharides
Synthesis of P0.1) By the same reaction procedure as in Synthesis Example 1, only the charged amount of N- (6-isocyanatohexyl) cholesterylcarbamate was 0.198 g (0.357 g).
mmol), CHP0.1 was synthesized. ¹ H-N
From the MR spectrum, the degree of substitution of the cholesterol group per 100 monosaccharides was calculated from the peak area derived from the cholesterol group and the peak area derived from the pullulan.
As a result, the degree of substitution of cholesterol groups per 100 monosaccharides was 0.1.

Synthesis Example 3 <A pullulan-cholesterol derivative (hereinafter C) having 0.05 cholesteryl groups introduced per 100 pullulan monosaccharides
Synthesis of HP0.05) By the same reaction procedure as in Synthesis Example 1, only the charged amount of N- (6-isocyanatohexyl) cholesterylcarbamate was reduced to 0.099 g (0.17 g).
8 mmol) to synthesize CHP0.05. ¹ H
From the NMR spectrum, the degree of substitution of the cholesterol group per 100 monosaccharides was calculated from the peak area derived from the cholesterol group and the peak area derived from the pullulan. As a result, the degree of substitution of cholesterol groups per 100 monosaccharides was 0.05.

Synthesis Example 4 <Pullulan-cholesterol derivative (hereinafter CHP) having 10 cholesteryl groups introduced per 100 pullulan monosaccharides
10) by the same reaction procedure as in Synthesis Example 1.
Only 29.7 g (53.6 mmol) of-(6-isocyanatohexyl) cholesteryl carbamate was charged.
Instead, CHP10 was synthesized. ^{From the 1} H-NMR spectrum, the degree of substitution of the cholesterol group per 100 monosaccharides was calculated from the peak area derived from the cholesterol group and the peak area derived from the pullulan. As a result, 1
The degree of substitution of cholesterol groups per 100 monosaccharides was 10.

Synthesis Example 5 <Pullulan-cholesterol derivative having 15 cholesteryl groups introduced per 100 pullulan monosaccharides (hereinafter referred to as CHP)
15) by the same reaction procedure as in Synthesis Example 1.
Only the charged amount of-(6-isocyanatohexyl) cholesteryl carbamate was 49.5 g (89.3 mmol).
Instead, CHP15 was synthesized. ^{From the 1} H-NMR spectrum, the degree of substitution of the cholesterol group per 100 monosaccharides was calculated from the peak area derived from the cholesterol group and the peak area derived from the pullulan. As a result, 1
The degree of substitution of cholesterol groups per 00 monosaccharide was 15.

Synthesis Example 6 <Mannan-cholesterol derivative having 0.9 cholesteryl groups introduced per 100 mannan monosaccharides (hereinafter referred to as C
Synthesis of HM> Pullulan was converted to mannan (average molecular weight, 85000) 26.2 by the same reaction procedure as in Synthesis Example 1.
g, and the charged amount of N- (6-isocyanatohexyl) cholesteryl carbamate was changed to 1.08 g (1.95 m
mol), the charge amount of pyridine was changed to 19.6 mL, and the charge amount of dimethyl sulfoxide was changed to 320 mL.
1.5 g of mannan-cholesterol derivative was synthesized. From ¹ H-NMR and IR measurements of the product, it was confirmed that the obtained compound was mannan-cholesterol (CHM). ^{From the 1} H-NMR spectrum, the degree of substitution of the cholesterol group per 100 monosaccharides was calculated from the peak area derived from the cholesterol group and the peak area derived from the mannan. As a result, the degree of substitution of cholesterol groups per 100 monosaccharides was 0.9.

Synthesis Example 7 <Synthesis of Tristrimethylsiloxysilylpropylcarbamate pullulan (hereinafter abbreviated as TSP) having 1.7 tristrimethylsiloxysilylpropyl groups introduced per 100 pullulan monosaccharides> Pullulan (average molecular weight, 10
(8000) was dissolved in 300 mL of N-methylpyrrolidone, 0.01 g of triethylamine was added as a catalyst, 0.7 g of tristrimethylsiloxysilylpropyl isocyanate was added dropwise, and the mixture was reacted at 100 ° C. for 2 hours. The reaction solution was poured into acetone, and the resulting precipitate was washed with methanol and dried to obtain 50 g of pullulan tristrimethylsiloxysilylpropylcarbamate. In addition,
The degree of substitution of the tristrimethylsiloxysilylpropyl group per 100 monosaccharides of pullulan in this product was calculated based on the elemental analysis value, and was 1.7.

Example 1 <Test for Evaluating Flavor Retention of CHP 0.9> 0.1% by weight of CHP 0.9 synthesized in Synthesis Example 1, 1% by weight of ethanol,
Limonene 0.01% by weight, methyl paraben 0.1% by weight,
A sample prepared by mixing 98.79% by weight of ion-exchanged water was dropped on the filter paper, and the intensity of the fragrance evaporating from the filter paper was measured using an odor sensor SF105A {Kyoku Yakuko Co., Ltd.}.
The measurement was performed after 0 minute and 60 minutes in a 0 ° C. environment, and the change in the frequency (Hz) after 60 minutes is shown in Table 1 as a relative ratio. The odor sensor SF105A captures the fragrance molecules on the surface of the vibrator and measures the frequency of the vibrator at that time. In this evaluation test, the larger the relative ratio of the frequency change, the better the fragrance retention.

Example 2 <Test for Evaluating Flavor Retention of CHP0.1> Instead of CHP0.9 synthesized in Synthesis Example 1, CHP0.
Example 1 was repeated except that No. 1 was used. Table 1 shows the results.

Example 3 <Test for Evaluation of Perfume Retention of CHP0.05> CHP synthesized in Synthesis Example 3 in place of CHP0.9 synthesized in Synthesis Example 1
The same procedure as in Example 1 was performed except that 0.05 was used.
The results are shown in Table 1.

Example 4 <Evaluation test of CHP10 for fragrance retention> C synthesized in Synthesis Example 1
The same procedure as in Example 1 was performed except that CHP10 synthesized in Synthesis Example 4 was used instead of HP0.9. Table 1 shows the results
It was shown to.

Example 5 <Evaluation test of CHP15 for fragrance retention> C synthesized in Synthesis Example 1
The same procedure as in Example 1 was performed except that CHP15 synthesized in Synthesis Example 5 was used instead of HP0.9. Table 1 shows the results
It was shown to.

Example 6 <Test for Evaluating Flavor Retention of CHM> CHP synthesized in Synthesis Example 1
The same procedure was performed as in Example 1 except that CHM synthesized in Synthesis Example 6 was used instead of 0.9. The results are shown in Table 1.

Example 7 <Test for evaluating the fragrance retention of TSP> CHP synthesized in Synthesis Example 1
The same procedure was performed as in Example 1 except that the TSP synthesized in Synthesis Example 7 was used instead of 0.9. The results are shown in Table 1.

Comparative Example 1 <Test for Evaluating Flavor Retention of Pullulan> CH synthesized in Synthesis Example 1
All procedures were performed in the same manner as in Example 1 except that commercially available pullulan (trade name: Pullulan PF20, manufactured by Hayashibara Shoji Co., Ltd., molecular weight: 200,000) was used instead of P0.9. The results are shown in Table 1.

Comparative Example 2 <Test for Evaluation of Perfume Retention of Diethylene Glycol> The procedure of Example 1 was repeated except that commercially available diethylene glycol was used instead of CHP 0.9 synthesized in Synthesis Example 1. The results are shown in Table 1.

Comparative Example 3 <Evaluation test of fragrance retention without blending of fragrance> Example 1 was repeated except that CHP0.9 synthesized in Synthesis Example 1 was not used (not blended).
And all were performed in the same manner. The results are shown in Table 1.

[0062]

[Table 1]

As a result of Examples 1 to 7 and Comparative Examples 1 to 3 shown in Table 1, it was found that the fragrance containing the polysaccharide derivative having a hydrophobic group had excellent fragrance retention.

Example 8 <Sensitivity Evaluation Test of Perfume Retention (CHP0.9) -Containing Detergent Composition> {Preparation of Perfume Retention Agent (CHP0.9) -Contained Detergent Composition} First, as a fragrance 1.58% by weight of orange oil, 2.63% by weight of bergamot oil, 8.42% by weight of rose oil, 10.53% by weight of phenylethyl alcohol, 2.11% by weight of jasmine absolute, 2.11% by weight of hexylcinnamic aldehyde 5.26% by weight, Lilyal 3.16% by weight, α-ionone 4.21% by weight, γ
2.11% by weight of methylyonone, 0.84% by weight of iris, 6.32% by weight of sandalwood oil, 2.11% by weight of vetiver oil, 10.53% by weight of celestelide, 8.10% by weight of heliotropin. 42% by weight, 5.26% by weight of pearlride, 9.47% by weight of coumarin, 1.05% by weight of ethyl vanillin, 0.20% by weight of vanillin,
2.5 g of a fragrance composition having a composition ratio of benzyl benzoate of 2.11% by weight and diethyl phthalate of 13.68% by weight was prepared. The perfume composition contains 0.5% by weight, and polyoxyethylene (EO) is used as a surfactant.
3) 16% by weight of sodium lauryl ether sulfate, 2% by weight of diethanolamide laurate, 3% by weight of amidopropyl betaine laurate, 1% by weight of ethylene glycol distearate, and 0.1% of sodium benzoate.
55% by weight, 0.1% by weight of dibutylhydroxytoluene
And CHP synthesized in Synthesis Example 1 as a flavoring agent.
500 g of a CHP0.9-containing cleaning composition containing 0.5% by weight of 0.9 and the remaining weight% of water was prepared. The prepared CHP0.9-containing cleaning composition exhibited a uniform appearance, and could be used as a cleaning composition without any problem.

{Preparation of a Hair Wash Test Sample Using the Perfume Preservative (CHP 0.9) -Containing Detergent Composition}
After preparing the 9-containing detergent composition, a bundle of uniform human hair prepared using the CHP0.9-containing detergent composition (20 g)
Was subjected to a hair washing and washing treatment. The washing and drying conditions at this time are as follows. First, a bundle of human hair (20 g) was immersed in warm water at 36 ° C. for 20 seconds to sufficiently adjust the hair to water, and then washed with the above-mentioned cleaning composition (3 g) for 3 minutes. Thereafter, the hair was rinsed three times with 3 liters of warm water at 36 ° C., rinsed and dried for 4 hours to obtain a hair washing test sample. << Preparation of comparative hair wash test sample >> The following work was performed in parallel with the above work. First, the aforementioned fragrance (CHP)
0.9) CHP 0.9 from the components of the contained detergent composition
500 g of a comparative detergent composition was prepared in the same mixing ratio except that only the components were not contained. Except that this comparative detergent composition was used in place of the CHP0.9-containing detergent composition, all were the same as in {Preparation of a hair wash test sample using a fragrance preservative (CHP0.9) -containing detergent composition} And a hair washing test sample for comparison was obtained.

{Test for Sensory Evaluation of Flavor Retention of Hair Washing Test Samples Using the Detergent Composition Containing Fragrance (CHP0.9)} The test was performed by a specialized panel using a hair wash test sample using the agent composition and a comparative hair wash test sample. At this time, compared with the comparative hair wash test sample, the panel dictated an impression about the scent retention of the hair wash test sample using the detergent composition containing a fragrance (CHP 0.9), and this was used as a fragrance ( A hair wash test sample using the CHP 0.9) -containing cleaning composition was evaluated for its fragrance retention. In this sensory evaluation test, a result was obtained that the panel showed that the improvement in perfumery was sufficiently detected for a hair wash test sample using the detergent composition containing a perfume preservative (CHP 0.9).

Example 9 <Test for sensory evaluation of perfume-retaining property of detergent composition containing fragrance (CHP0.1)> Instead of CHP0.9 synthesized in Synthesis Example 1, CHP0.1 synthesized in Synthesis Example 2 was used. Except having used, all it carried out similarly to Example 8. In this sensory evaluation test, a result was obtained that the panel showed that the improvement in perfume retention was sufficiently sensed for the hair wash test sample using the detergent composition containing the perfume retainer (CHP0.1).

Example 10 <Test for Sensory Evaluation of Perfume Retention Property of Detergent Composition Containing Fragrance (CHP0.05)> Instead of CHP0.9 synthesized in Synthesis Example 1, CHP0.05 synthesized in Synthesis Example 3 was replaced with CHP0.05 synthesized in Synthesis Example 1. Except having used, all it carried out similarly to Example 8. In this sensory evaluation test, a result was obtained that the panel showed a slight improvement in the fragrance retention of the hair wash test sample using the fragrance retention agent (CHP0.05) -containing cleaning composition.

Example 11 <Perfection evaluation test of perfume-retaining property of a detergent composition containing a perfume-retaining agent (CHP10)> Except that CHP10 synthesized in Synthesis Example 4 was used instead of CHP0.9 synthesized in Synthesis Example 1. Example 8
And all were performed in the same manner. In this sensory evaluation test, the flavoring agent (C
As for the hair wash test sample using the cleaning composition containing HP10), the result was obtained that the panel showed that the improvement in perfumery was sufficiently recognized.

Example 12 <Test for sensory evaluation of fragrance retention of detergent composition containing fragrance (CHP15)> Except that CHP15 synthesized in Synthesis Example 5 was used instead of CHP0.9 synthesized in Synthesis Example 1. Example 8
And all were performed in the same manner. In this sensory evaluation test, the flavoring agent (C
For the hair wash test sample using the HP15) -containing cleaning composition, the result was that the panel showed a slight improvement in perfume retention.

Example 13 <Perfection evaluation test of perfume-retaining agent composition containing fragrance (CHM)> A CHM synthesized in Synthesis Example 6 was used instead of CHP 0.9 synthesized in Synthesis Example 1. All operations were performed in the same manner as in Example 8. In this sensory evaluation test, a result was obtained that the panel showed a slight improvement in the fragrance retention of a hair wash test sample using the fragrance retaining agent (CHM) -containing cleaning composition.

Example 14 <Test for Sensory Evaluation of Flavor Retention Property of Detergent Composition Containing Perfume Preservative (TSP)> Except that the TSP synthesized in Synthesis Example 7 was used instead of CHP 0.9 synthesized in Synthesis Example 1. All operations were performed in the same manner as in Example 8. In this sensory evaluation test, a result was obtained that a slight improvement in the fragrance retention was perceived from the panel for a hair wash test sample using the fragrance-preserving agent (TSP) -containing cleaning composition.

As described above, it was confirmed that the panels of Examples 8 to 14 improved the fragrance retention. Among them, CHP0.05 of Example 10, CHP15 of Example 12, CHM of Example 13, and TSP of Example 14 were slightly inferior to the other Examples. This is because CH
In the case of P0.05, it was presumed that this was because the fragrance was washed off after washing and rinsing, and the fragrance retention after drying was reduced.
In the case of CHP15, it was presumed that a strong film was formed, the barrier ability was too high, and the volatilization of the fragrance was suppressed. In addition, it was presumed that CHM and TSP had a weaker film-forming ability than CHP, and that the fragrance could not be sufficiently retained. However, since the effect of improving the fragrance retention was observed in all cases, it was sufficiently confirmed that the hydrophobic group-containing polysaccharide derivative can be used as a fragrance.

From these results, the perfume preservative of the present invention (1) is remarkably excellent in perfume preservation effect, and exhibits an effect as a perfume preservative in order to maintain the initial fragrance for a long time.
(2) The skin external preparation composition of the present invention has an effect of maintaining a fragrance for a long period of time. (3) The cleaning composition of the present invention not only maintains the scent for a long time, but also imparts a scent to the object to be cleaned,
It has the effect of maintaining the fragrance retention after drying. (4) The detergent composition containing the fragrance of the present invention does not wash off the fragrance and fragrance of the object to be washed even after washing and rinsing, and even when dried. It has been found that it has an excellent effect of suppressing volatilization of the fragrance and increasing the fragrance retention after drying.

Claims (8)

[Claims] 1. A fragrance comprising a polysaccharide derivative having a hydrophobic group. 2. A fragrance comprising a hydrophobic group-containing polysaccharide derivative obtained by introducing 0.1 to 10 hydrophobic groups per 100 polysaccharide monosaccharides. 3. A fragrance composition comprising the fragrance according to claim 1 or 2. 4. The fragrance composition according to claim 3, which is for pets. 5. An external preparation for skin containing the fragrance according to claim 1 or 2. 6. The external composition for skin according to claim 5, which is for pets. 7. A detergent composition containing the fragrance according to claim 1 or 2. 8. The cleaning composition according to claim 7, which is for pets.