JPS6354499A - Aroma holding composition - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention provides a novel fragrance-retaining composition, more specifically, a novel fragrance-retaining composition which has a high fragrance retention tV and which does not reduce its fragrance-retaining properties even when added to detergents and cosmetics. The present invention relates to a fragrance composition. .

BACKGROUND OF THE INVENTION Various detergents, cosmetics, bath additives, etc. usually contain fragrances to provide a pleasant sensation during or after use.

By the way, when fragrances are added to these products, they are usually used in combination with so-called fragrance preservatives so that the fragrance remains for a certain period of time even after use.

Conventional fragrance preservatives include solvents such as benzyl benzoate, dialkyl phthalate, barcolin, limonene dimer, alkylene glycol, polyalkylene glycol, alkyl citrate, dialkyl adipate, Mil-, Peru balsam, and true balsam. ,
Musks, civet, vanillin, hydroxycitronellal, olibanum, vetiver, benzylisoeugenol.

Ampret, benzoin, lapdanum, talarisage, cinnamic alcohol, iris, styrax, costus, coumarin, methylnaphthyl ketone, cinnamyl cinnamate, ethyl cinnamate, β-naphthol ether, anhacris, rosephenone, oakmoss, dimethylhydroquinone, elemi , mastic, indole, patchouli, basil, cedar, musk ketone,
Retentive fragrances such as diphenylmethane, solid carriers such as fluorite, zeolite, starch, Merck, plastics, clay, and cellulose are used.

However, the ability of these fragrance preservatives to retain a residual fragrance is not necessarily sufficient, and when they are used in combination with detergent components, they have the disadvantage that their fragrance retention properties are significantly reduced.

Problems to be Solved by the Invention The purpose of the present invention is to overcome the above-mentioned drawbacks of conventional fragrance preservatives, to exhibit excellent residual fragrance retention ability, and to maintain fragrance retention when mixed with detergent ingredients. An object of the present invention is to provide a fragrance preservative composition that maintains the following properties.

Means for Solving the Problems As a result of various studies, the present inventors discovered that the purpose could be achieved by using a water-soluble chitin visiting agent as a fragrance preservative, and based on this knowledge, the present inventors developed the present invention. He came up with an invention.

That is, the present invention provides a fragrance composition characterized by containing a water-soluble chitin derivative as a fragrance preservative together with a fragrance.

Chitin has N-acetylated-D-glucosamine as β-1
, 4-bonded polymer compound, which is known to exist in large amounts in the natural world, such as in arthropods, molluscs, and fungal hyphae and spores. The resulting product is known as chitosan.

By the way, chitin and chitosan have a chemical structure similar to that of cellulose, but their resistance to chemicals is far greater than that of cellulose, and they also contain reactive groups such as acetamido and amino groups in their molecules. Although it is very interesting as an industrial raw material, it is not widely used in reality, so expanding the scope of its use is one of the important challenges for chitin. It had become.

In the present invention, a water-soluble substance derived from chitin, that is, a water-soluble chitin derivative, is used as a fragrance preservative.

Chitin has the chemical structure elfL shown by the general formula, for example, by crushing the shells of crabs, shrimps, krill, etc., removing calcium carbonate with hydrochloric acid, then removing proteins and other impurities with sodium hydroxide, and then washing with water. By drying, it can be obtained as a white flaky substance.

Also, chitosan, which is a deacetylated product of this.

For example, it is a substance obtained as a white flake-like substance by treating chitin with an alkali, and is also available as a commercial product (for example, trade name "Fronac NJ", manufactured by Kyowa Yushi Kogyo).

As the water-soluble chitin derivative used in the present invention, chitin or chitosan can be decomposed by nitrite decomposition, gypsum decomposition, chlorine decomposition, etc.
Hydrophilic groups introduced into chitin or chitosan, water-soluble chitosan with controlled deacetylation degree, water-soluble salts of chitosan and organic or inorganic acids It can also indicate water-soluble substances.

Examples of the low-molecular-weight chitin or chitosan include water-soluble oligomers containing two or more glucosamine units, and examples of the water-bathable chitosan include deacetylation degrees of 40 to 40.
60% water-soluble chitosan, and the water-soluble salt of chitosan is a salt of chitosan with an organic acid such as acetic acid, malic acid, citric acid, or ascorbic acid or an inorganic acid such as hydrochloric acid, sulfuric acid, or phosphoric acid. can be mentioned.

In addition, examples of derivatives having hydrophilicity include -general formula [wherein, n:>■ R,: -H, -COCH3 or +KO-)--4PO
+H11z+ (However, tl-0~5.m1=o~5゜t+m≠0) R2 knee H or +EO-), 2-4PO+1Z12H (
However, 12"0~5, R2-0~5, t2+m2
≠R5: -H or +EO+t3・+PO+rQ3H(
However, 15=O~5, R5-0~5.15 +m3
≠, where KO represents an oxyethylene chain, PO represents an oxypropylene chain, and.

The order of the combination of go and PO does not matter; for example, maf, D
- PO may be added to the glucosamine skeleton, and then EO may be added, or EO and PO may be added randomly, and each D-glucosamine skeleton connected to Rj + R2+ R3+ nj a n2
* R5t t1+ t2 at3 may be the same or different respectively]
Polyoxyprobile/chitin or chitosan, general formula [where n::>1 R4: -H or -cocu3 R5: -H, -CH2COOH2-CH3COONa
.

-(!)12C+OOK or -cn2cooNFIAR
6: -H, -CH2COOH2-(H2COON&
.

-cm2coox or -cH2cooNB4 V),
Both Rs and R6 are not -H, and in each bonded D-glucosamine skeleton, R4, R5,
R6 may be the same or different, respectively. Carboxymethyl chitin or chitosan with the general formula [where n:
is 0R2 -H1Na r K or -NH4) 0R5 R6: -H or -P-0 (R5 and R4 are -I'l, N
a, 0R4 or -NH4) 0R5 R9 knee H or -F-0 (R5 and 4 are -H, Na, 0M6 or -NH4) 0M7 Ma -H*Na, K or -NH4) However, in each of the linked D-glucosamine skeletons, R7#Re#R9=I'tto may be the same or different, but R8 and R9 are -H
Phosphorylated chitin or chitosan with the general formula [wherein n:〉l R11 nee H, -COCH; NH4)0M1
0 ■ R12 knee H or -s=o (Mlg is -H, Na, K or -NH4) 7M11 R13 knee H or -s-0 (Mu is -1 (, Na, K or -NH4) ?M12 R14 knee H1−COC!H3 or −S=lIO(M1
2 is -H, Na.

K or -NH4), and R11, R12, R131Rj4 may be the same or different in each bonded D-glucosamine skeleton] Sulfated chitin or chitosan, with the general formula , n: > 1 R17: -H or -(:!0CH3 R18 knee H or -cH2-CH-CH20HH Fj19: -H or -ca2- CH-CH20H
dihydropropyl chitin or chitosan, represented by the general formula [where n:>1 0H,0 (M2S is Na, K or -IJH4) 0HO (M14 is Na, K or -NH4) R20 and RH do not become -H at the same time] R2-hydroxypropylsulfonic acid chitosan and the like can be mentioned.

Water-soluble chitin or chitosan having these hydrophilic groups can be obtained, for example, by the following production method.

Polyoxyethylene polypropylene glycol chitin or chitosan is alkali chitin or chitosan,
Chlorhydroxyethylene, chlorohydroxypropylene, ethylene oxide or propylene oxide at room temperature and pressure or at 50-60°C for 1-5Ks+/a+! It is obtained by reacting G under pressure.

Carboxymethyl chitin or chitosan can be obtained by reacting alkali chitin or chitosan with monochloroacetic acid at room temperature and pressure.

Phosphorylated chitin or chitosan can be obtained by reacting chitin or chitosan dissolved or suspended in methanesulfonic acid with niline pentoxide under cooling. This method is described in 1. For example, Proceedings of the 48th Autumn Annual Meeting of the Chemical Society of Japan
, page 570 (Norio Nishi et al.).

Sulfated chitin or chitosan can be obtained by reacting chitin or chitosan activated in pyridine with a 503-pyridine complex [Journal of the American Chemical Society (J, Am, Chem, So.
c, ) J Vol. 81, pp. 1764-1766 (
1959)].

Dihydroxypropyl chitin or chitosan can be obtained by ring-opening and adding shrimp chlorohydrin to alkali chitin or chitosan at high temperatures.

N2-Hydroxyglobylsulfonic acid chitosan is produced by adding glycidyl sulfonic acid to chitosan at high temperature under an alkali catalyst.
It is obtained by adding under pressure.

The water-soluble chitin derivatives in the present invention may be used alone or in combination of two or more. Among these, partially deacetylated water-soluble chitosan is particularly suitable.

In the composition of the present invention, the water-soluble chitin derivative is preferably blended with the perfume in a weight ratio of 1:10 to 10:1, preferably 1:2 to 2:1. If the amount of this water-soluble chitin derivative is less than this, sufficient fragrance retention cannot be obtained, and if it is more than this, the physical properties as a whole will deteriorate when blended into detergents or cosmetics.

There is no particular restriction on the fragrance that can be used in combination with this fragrance preservative to provide a fragrance composition with a high residual odor, and may be either a natural fragrance or a synthetic fragrance. Examples of natural fragrances include orange oil, lemon oil, lime oil, butygrain oil, yuzu oil, neroli oil, bergamot oil, lavender oil, lavandin oil,
Avinis oil, Pei oil, bore rose oil, ylang ylang oil, citronella oil, geranium oil, peppermint oil, peppermint oil, spearmint oil, eucalyptus oil, lemongrass oil,
Patchouli oil, jasmine oil, loin oil, cedar oil, beef
bar? 'L galbanum oil, oakmoss oil, pine oil,
Essential oils such as camphor oil, sandalwood oil, camphor oil, turpentine oil, clove oil, clove leaf oil, cassia oil, nutmeg oil, cananga oil, and thyme oil; Animal flavorings are used. Examples of synthetic fragrances include linalool, linalyl acetate, geraniol, citronellol, various aliphatic aldehydes from 06 to 12, phenylethyl alcohol, benzyl acetate, geranyl acetate, geranyl formate, vanillin, nitro musks, galacturide, and tonalide. ,
Examples include pentalide, Santarex, amyl acetate, amyl acetate, γ-undecalactone, ethyl methylphenylglycidate, heliotropin, and the like.

Each of these fragrances may be used alone, or two or more types may be used as a blended fragrance.

The composition of the present invention may optionally contain auxiliaries, diluents, and additives, such as enzymes and pigments, which are commonly used in perfume compositions, to the extent that they do not impair the purpose of the present invention.

Antioxidants, preservatives, bactericides, and other active ingredients,
For example, crude drugs, vitamins, nutrients, fats and oils, and effect agents 1 such as bleaches, deodorizers, softeners, etc. can be added.

Effects of the Invention The fragrance-retaining composition of the present invention is a fragrance containing a water-soluble chitin derivative, has excellent fragrance retention, and is suitable for use in laundry detergents, shampoos, soaps, and other bath cleaners. ,
Products containing fragrances, such as household cleaners, air fresheners, cosmetics such as eaute cologne, splash cologne, thiotranthe cologne, creams, lotions, hair conditioners, and antiperspirants, bath salts, bubble baths, and other bath additives. It is particularly suitable for use in cleaning agents.

Example Next, the present invention will be explained in more detail with reference to Examples.

Incidentally, the strength of the residual fragrance was determined by sensory evaluation by six panelists specializing in fragrance using the following evaluation criteria, and the average scores were compared.

Evaluation criteria for strength of lingering scent 5 points Strong lingering scent 4I Afterglow and strong 3I There is a lingering scent 21 There is a lingering scent 1 point: No lingering scent 0# No lingering scent at all The evaluation method for each product is as follows.

(1) Shampoo: Hair is washed using the half-head method (dividing the hair into right and left parts at the center and using samples for comparison) and evaluating the hair using two points.

The strength of the fragrance after wiping off moisture The strength of the fragrance after drying the hair 2) Granular detergent, liquid detergent, fabric softener If you use fabric softener, just dehydrate and dry it, but if you use fabric softener, add it after rinsing and dehydrate it.
After drying, each sample is evaluated with 2 points.

Strength of incense when drying after dehydration Intensity of incense after drying and when soaking 3) Soaps, bath salts: Half-hand method (using samples for comparison on the right and left hands), 2 points evaluate.

Strength of incense immediately after wiping off water Intensity of scent 3 hours after wiping off water 4) Eau de Cologne: Using the half-hand method, a comparative sample is attached to the right arm and left arm and evaluated on a two-point scale.

Fragrance strength after 1 hour after application.Fragrance strength after 8 hours after application.Example 1 Green floral (1), (10 and (I[D') having the compositions shown in Table 1. A shampoo composition containing these ingredients and having the composition shown in Table 2 was prepared, and its fragrance lingering property after use was examined.The results are shown in Table 2.

As can be seen from Table 1 and Table 2, the shampoo composition containing the fragrance-retaining composition in which a water-soluble chitin derivative is blended with the fragrance in advance has excellent fragrance retention after use, and also has excellent fragrance retention after use. Even if a chitin derivative is blended into a shampoo composition, the effect of improving fragrance retention is small.

Example 2 Floral Puke (goods), (to), and (b) having the compositions shown in Table i3 were prepared, and a soap composition containing these with the composition shown in Table 4 was prepared, and its residual fragrance was investigated. . The results are shown in Table 4.

Table 3 Example 3 Floral Puke (1), (It), and (10) were prepared, and a granular detergent composition containing them with the composition shown in WJs was prepared, and the residual fragrance after use was investigated. Ta. As a result, the granular detergent compositions of Examples had excellent fragrance retention.

Table 5 [Note] Floral Puke (ri; Mixture of 60% by weight of detergent fragrance and 40% by weight of water-soluble chitin derivative Floral Puke (■); Mixture of 60% by weight of detergent fragrance and 4oH qb of diethyl phthalate (2); For detergent fragrance only Example 4 Perfume toner (1), (II) and (Ill) were prepared,
A fabric softener composition containing these components having the composition shown in Table 6 was prepared, and the odor lingering property (f) after use was investigated. .

〔note〕

Fragrance Softener 7 Toner (■); Mixture of fragrance softener 50% by weight and diethyl phthalate 50% by weight Fragrance softener (2); Fabric softener only Example 5 Fragrance bath salt (I), ( II) and ((2) were prepared, and a bath additive composition containing these with the composition shown in Table 7 was prepared, and the residual fragrance after use was investigated.As a result, the bath additive composition of the example The product had excellent lingering scent.

Table 1 [Note] Flavored bath salt (1); Mixture of 80% by weight of fragrance for bath salts and 20% by weight of water-soluble chitin derivative; 80% by weight of fragrance for bath salts and 20% by weight of diethyl phthalate Mixture of fragranced bath salts (2); perfume for bath additives only Example 6 Eau de cologne composition containing all the fragrances fan de cologne (I), (l[) and @) and having the composition shown in Table 8 was prepared and its residual odor after use was investigated.

As a result, the cologne compositions of Examples had excellent fragrance retention.

Table 8 [Note] Mixture fragrance fan de cologne with N amount Q (■); fragrance for eau de cologne 90
Mixture of weight fraction and 10% by weight of diethyl phthalate

Claims (1)

[Claims] 1. A fragrance-preserving composition characterized by containing a water-soluble chitin derivative as a fragrance preservative together with a fragrance.