JP6178609B2 - Liquid fragrance composition - Google Patents

Description

  The present invention relates to a liquid fragrance composition and a liquid fragrance article. Furthermore, it is related with the liquid fragrance | flavor composition for textiles, and the liquid fragrance | flavor article | item filled with it.

  Laundry is performed when dirt or odor adheres to textiles including clothing, or in consideration of hygiene. However, recently, since the clothes are less likely to get dirty outdoors, there is an increasing demand for deodorants that can be easily processed for clothes with an unpleasant odor such as body odor and tobacco odor. In connection with these requirements, spray-type treatment agents that can be deodorized and sterilized by spraying a solution having a deodorizing effect on textiles have been developed. Spray-type treatments are used to remove odors that adhere to fashionable clothes, suits, sweaters, shoes and bedding, mattresses, fabric sofas, carpets, etc. It's being used.

  On the other hand, the lifestyle habit of actively scenting clothing is spreading for the purpose of enjoying the scent of the clothing being worn. For example, in commercial softener compositions and detergent compositions, products with a full fragrance property are sold.

  In order to solve the problem of unpleasant odors attached to textile products such as body odor and tobacco odor, a method of masking unpleasant odors using perfume or the like is well known. Also, unlike masking, many techniques have been disclosed so far regarding techniques for finding the cause of unpleasant odors and deodorizing them by chemically treating the causative substances.

  As for the fragrance, it is described that a deodorant component such as a plant extract is blended with a deodorant as disclosed in Patent Document 1 and Patent Document 2. Patent Documents 3 and 4 disclose liquid deodorant compositions containing a quaternary ammonium compound or an amine oxide compound. Patent Document 5, Patent Document 6 and the like are known to suppress amine odor and fatty acid odor by providing the composition with a buffering ability. Patent Document 6 discloses sodium citrate and potassium phosphate as buffering agents.

  Techniques using polyhydroxyamine compounds, such as Patent Document 7, Patent Document 8, Patent Document 9, and Patent Document 10, are known as techniques related to deodorants having buffering ability.

  Examples of the approach from the fragrance component include Patent Document 11 and Patent Document 12, which describe a deodorant composition comprising the polyhydroxyamine compound and a fragrance component having a non-aldehyde structure as the fragrance component. ing.

JP-A-61-193665 JP-A-4-257514 JP 2000-325454 A JP 2006-102477 A JP 2001-040581 A JP 2007-0777545 A JP 2006-320711 A JP 2006-320712 A JP 2007-160071 A JP 2009-028071 A JP 2008-136841 A JP 2007-300963 A

  Since masking of unpleasant odors by fragrances does not basically eliminate the odor of the target, there is a problem that the odor of the designed flavoring composition is different from that of the designed fragrance composition. May change. Therefore, there is a method of increasing the fragrance concentration to increase the fragrance so that the unpleasant odor is not felt. However, there is a concern that the strong fragrance causes a new unpleasant sensation. On the other hand, when using a deodorant component and a fragrance | flavor component together, there exists a possibility that a mutual action may be offset. This fact restricts the perfume ingredients that can be used in combination, and reduces the degree of freedom in adjusting the fragrance.

  The subject of the present invention relates to the scenting of textiles, in addition to being able to effectively impart fragrance to textiles by having a deodorizing performance against unpleasant odors attached to textiles, and various An object of the present invention is to provide a liquid fragrance composition that does not modulate the scent by storage while using a fragrance component.

The present invention
(A) Phosphoric acid or a salt thereof (hereinafter referred to as “component (a)”) in terms of acid type compound is 0.01% by mass or more and 0.9% by mass or less (b) The molecular weight in terms of acid type compound is 90 or more, A polycarboxylic acid of 500 or less or a salt thereof (hereinafter referred to as “component (b)”) in terms of an acid type compound is 0.005% by mass or more and 0.5% by weight or less,
(C) 0.01% by mass or more and 1% by mass or less of a nonionic surfactant represented by the following general formula (I) [hereinafter referred to as component (c)]
(D) A fragrance component [hereinafter referred to as (d) component] is contained in an amount of 0.005 mass% to 0.5 mass%, and water,
The total content of (a) and (b) is 0.02% by mass or more and 1% by mass or less, and the pH at 25 ° C. is 4.0 or more and less than 6.0,
The present invention relates to a liquid flavoring agent composition.
R ¹ -X-[(EO) _s (PO) _t ] -R ² (I)
[In Formula (I), R ¹ is an alkyl group or alkenyl group having 10 to 22 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X is —O—. Or -COO-, EO is an ethyleneoxy group, PO is a propyleneoxy group, s and t represent the average number of added moles, t is 0 or more and 3 or less, and the sum of s + t is 5 or more 15 or less. When both (EO) and (PO) are included, (EO) and (PO) may be random addition or block addition, and there is no restriction on the order of addition. ]

  Moreover, this invention relates to the liquid fragrance | flavor articles | goods formed by filling the container with a manual spray apparatus with the liquid fragrance | flavor composition of the said invention.

  According to the present invention, unpleasant odor adhering to the textile product can be reduced or deodorized when the textile product is scented, while the degree of freedom of the fragrance component used for the fragrance is high, and the scent is modulated by storage. There is provided a fragrance-controlling agent composition for a fiber product that has a small amount of fragrance and is excellent. That is, according to the present invention, not only for the purpose of flavoring textile products for enjoying fragrance, but also for textile products with a bad odor or bad odor attached, because it has a deodorizing effect, the odor can be suppressed. Provided is a liquid fragrance composition that can be used for the purpose of fragrance not affected by the above. Moreover, despite having a deodorizing effect, a liquid fragrance composition having a higher degree of freedom of a fragrance component than in the prior art and less scent modulation after storage is provided. Furthermore, the liquid fragrance | flavor articles | goods which can be easily applied to a textile product by filling the container provided with the spray apparatus with the liquid fragrance | flavor composition of this invention are provided.

<(A) component: phosphoric acid or a salt thereof>
The component (a) of the present invention is phosphoric acid or a salt thereof. The salt is preferably an alkali metal salt. Since the liquid flavoring agent composition of the present invention is an aqueous composition containing water, phosphoric acid or an alkali metal phosphate is present in an ion-dissociated state. The ratio varies depending on the pH. As the phosphate, a salt selected from sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate and dipotassium hydrogen phosphate is preferable, and dipotassium hydrogen phosphate is more preferable.

  When preparing the composition of this invention, it is preferable to mix | blend (a) component as an alkali metal phosphate as a salt. Further, when preparing the composition of the present invention, the component (a) is preferably blended as an aqueous solution, and may be blended as an aqueous solution of the alkali metal phosphate, and further as an aqueous solution of dipotassium hydrogen phosphate. More preferable from the viewpoint of solubility. In the present invention, the phosphate may be a hydrate, but the content concentration in the composition is an anhydride and a concentration converted to phosphoric acid.

<(B) Component: Polycarboxylic acid or salt thereof>
(B) A component is polycarboxylic acid or its salt. The molecular weight of the component (b) is 90 or more, preferably 100 or more, more preferably 130 or more, still more preferably 150 when converted to an acid structure when it is anhydrous and converted to an acid structure. And 500 or less, preferably 300 or less, more preferably 250 or less, further preferably 100 to 300, and further preferably 130 to 250.

  Specifically, the component (b) is one or more selected from methylglycine diacetic acid, ethylenediaminetetraacetic acid, oxalic acid, succinic acid, fumaric acid, tartaric acid, malic acid, citric acid and salts thereof. Compounds are preferred. The component (b) is preferably a compound having a hydroxy group in the molecule, and more preferably a compound having one hydroxy group in the molecule. As the component (b), one or more compounds selected from tartaric acid, malic acid, citric acid and salts thereof are more preferable, and one or two or more compounds selected from citric acid and salts thereof are preferable. Further preferred. In the present invention, the polycarboxylic acid or a salt thereof may be a hydrate, but the content concentration in the composition is an anhydride and a concentration converted to the acid type.

  From the viewpoint of the odor of the composition itself, the salt of the component (b) is preferably an alkali metal salt, more preferably a salt selected from a sodium salt and a potassium salt.

  When the component (b) is blended in a solid form such as a powder, it is preferable that a part or all of the component (b) is citric acid (acid type compound) or a hydrate thereof, and further, the component (b) It is more preferable that all of these are citric acid or a hydrate thereof.

  Moreover, (b) component can also be mix | blended as aqueous solution which melt | dissolved in water. In that case, the pH of the aqueous solution at 25 ° C. is acidic, specifically, the pH is preferably 1 or more and 6 or less, and more preferably 5 or less. The aqueous solution concentration is 20% by mass or more and the saturation level or less in terms of acid type compound.

  It is preferable to adjust the pH of the composition of the present invention by using the component (a) and the component (b) in combination. In the present invention, a combination in which the component (a) is dipotassium hydrogen phosphate and the component (b) is citric acid is preferable from the viewpoint of adjusting pH. Moreover, in order to make pH into the target range, acidic aqueous solutions, such as hydrochloric acid aqueous solution, or alkaline agents, for example, alkaline aqueous solutions, such as potassium hydroxide and potassium hydroxide, can also be used.

<(C) component: nonionic surfactant>
The liquid fragrance composition of the present invention contains the following general formula (I) nonionic surfactant as the component (c) in order to sufficiently disperse the fragrance component and not change the fragrance tone by storage.
R ¹ -X-[(EO) _s (PO) _t ] -R ² (I)
[Wherein R ¹ is an alkyl group or alkenyl group having 10 to 22 carbon atoms, preferably an alkyl group, more preferably a linear alkyl group, and R ² is a hydrogen atom or 1 to 3 carbon atoms. X is —O— or —COO—, EO is an oxyethylene group, PO is an oxypropylene group, s and t represent the average number of moles added, and t is 0 or more. 3 or less, preferably 0 or more and 2 or less, more preferably 0, and the sum of s + t is 5 or more and 15 or less. When both (EO) and (PO) are included, (EO) and (PO) may be random addition or block addition, and there is no restriction on the order of addition. ]

As the component (c), for example, a compound having a structure represented by the following general formula (II) is more preferable.
_{^{R 1 -O (EO) s1 -}} (PO) t - (EO) s2 -H (II)
(In the formula, R ¹ , EO and PO are the same as above. T is the same as above, s1 and s2 represent the average number of added moles, s1 + s2 = s, s1 is 0 or more and 10 or less, s2 Is 5 or more and 15 or less, and the sum of s1 + s2 + t is 5 or more and 15 or less.)

(C) component is from a viewpoint of deodorant performance improvement,
(C1) Polyoxyethylene lauryl ether (X in the general formula (I) is —O—, the average added mole number s of ethyleneoxy groups in the general formula (I) is 6 or more and 12 or less, in the general formula (I) A non-ionic surfactant in which the average added mole number t of the propyleneoxy group is 0, R ^{1 in} the general formula (I) is a lauryl group, and R ² in the general formula (I) is a hydrogen atom)
(C2) Polyoxyethylene alkyl ether (X in the general formula (I) is -O-, the average addition mole number s of ethyleneoxy groups in the general formula (I) is 5 or more and 12 or less, in the general formula (I) A secondary alkyl group or an alkenyl group having an average addition mole number t of 0 of propyleneoxy group in general formula (I) and R ¹ in general formula (I) of 12 or more and 14 or less, preferably an alkyl group, general formula (I) Nonionic surfactant in which R ² is a hydrogen atom), and (c3) polyoxyethylene lauric acid ester methyl ether (X in general formula (I) is —COO—, ethylene in general formula (I) The average addition mole number s of the oxy group is 6 or more and 12 or less, the average addition mole number t of the propyleneoxy group in the general formula (I) is 0, R ¹ in the general formula (I) is a lauryl group, the general formula (I ) nonionic surface active R ² is methyl Motoko in Agent)
1 or more types of nonionic surfactant chosen from these are more preferable.

<(D) component; perfume component>
Examples of the fragrance component that is the component (d) used in the present invention include the fragrance described in “Basic knowledge of fragrance and fragrance, edited by Motoki Nakajima, published by Sangyo Tosho Co., Ltd., April 20, 2005”. Moreover, the fragrance | flavor of JP, 10-507793, A can be used.

Perfume ingredients are appropriately selected and used from the standpoints of fragrance quality and strength, and stability in softener systems.
Hereinafter, the compounds used as the perfume component of the component (d) of the present invention are classified into the categories shown in the perfume field and are as follows.

  Examples of the terpene compound include limonene, p-cymene, α-pinene, β-pinene, and β-caryophyllene. Among the terpene compounds, a compound known to those skilled in the art to function as a fragrance can be referred to as a terpene fragrance for convenience.

  As alcohol compounds, cis-3-hexenol, trans-2-hexenol, methyltrimethylcyclopentenylbutenol, dihydromyrcenol, l-menthol, phenylethyl alcohol, citronellol, geraniol, nerol, linalool, terpineol, tetrahydrolinalol, tetrahydro Geraniol, dimethylbenzyl carbinol, β-phenylethyl alcohol, benzyl alcohol, cinnamic alcohol, anis alcohol, farnesol, nerolidol, dimethylphenylethyl carbinol, trance-4-t-butylcyclohexanol, cis-4-t- Butylcyclohexanol, sandalmysol core (2-methyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol) (manufactured by Kao Corporation) , Bagudanoru (IFF Inc.), Jabanoru (Givaudan Co., Ltd.). Among alcohol compounds, a compound known to those skilled in the art to function as a fragrance can be referred to as an alcohol-based fragrance for convenience.

  As ester compounds, benzyl acetate, dimethylbenzyl carvinyl acetate, linalyl acetate, neryl acetate, o, t-butylcyclohexyl acetate, p, t-butylcyclohexyl acetate, citronellyl acetate, geranyl acetate, tetrahydrogeranyl acetate, terpenyl acetate, isobornyl acetate 1-menthyl acetate, tricyclodecenyl acetate, 2-phenylethyl acetate, 3-phenylpropyl acetate, styryl acetate, cis-3-hexenyl acetate, trans-2-hexenyl acetate, hexyl acetate, cinnamyl acetate, propionic acid Isobutyl, 2-phenylethyl propionate, citronellyl propionate, benzyl propionate, tricyclodecenyl propionate, geranyl propionate, allyl propionate, geranyl butyrate, citronellyl butyrate, isoamyl butyrate, butyric acid Amyl, allyl butyrate, phenoxyethyl isobutyrate, geranyl isobutyrate, geranyl isovalerate, ethyl caproate, allyl caproate, ethyl enanthate, allyl enanthate, ethyl octanoate, methyl anthranilate, cis-3-hexenyl benzoate Benzyl benzoate, amyl salicylate, isoamyl salicylate, benzyl salicylate, cis-3-hexenyl salicylate, hexyl salicylate, 2-phenylethyl salicylate, methyl dihydrojasmonate, coumarin, γ-octalactone, γ-undecalactone, γ Decalactone, γ-nonalactone, δ-nonalactone, δ-decalactone, δ-undecalactone, δ-dodecalactone, cyclopentadecanolide, cyclopentadecenolide (Havanolide, Filmenich), cycl Hexadecanolide, ambretolide, 11-oxa-16-hexadecanolide (Musk R-1, manufactured by Dibodan), 10-oxa-16-hexadecanolide (Oxalide, manufactured by Takasago International Corporation), 12-oxahexadecanolide, ethylene Examples thereof include brush rate and ethylene dodecanedioate (Musk C-14). Among the ester compounds, a compound known to those skilled in the art to function as a fragrance can be referred to as an ester-based fragrance for convenience.

  As aldehyde compounds, octanal, nonanal, decanal, undecanal, 10-undecenal, dodecanal, greenal, citral, citronellal, anisaldehyde, phenylacetaldehyde, phenylpropylaldehyde, cinnamic aldehyde, myracaldehyde, lilyal, lyral, dimethyltetrahydrobenzaldehyde , Α-amylcinnamic aldehyde, α-hexylcinnamic aldehyde, cyclamenaldehyde, vanillin, ethyl vanillin, heliotropin, helional, mandarin aldehyde, tripral, and bolenal II. Of the aldehyde compounds, compounds known to those skilled in the art to function as perfumes can be referred to as aldehyde perfumes for convenience.

As ketone compounds, florarozone, l-carvone, menthone, cis jasmon, geranylacetone, damascones, damasenones, α-dynascon, ionones, methyl ionones, β-methyl naphthyl ketone, iso-E super, raspberry ketone, maltol, ethyl maltol , Cachemelan (manufactured by IFF), 5-cyclohexedenon-1-one (Musk TM-II) 3- (pt-butylphenyl) -propylaldehyde, p-ethyl-2,2-dimethylhydrocinnamaldehyde 2-methyl-3- (p-methoxyphenyl) -propylaldehyde, pt-butyl-α-methylhydrocinnamic aldehyde, and the like. Of the ketone compounds, compounds known to those skilled in the art to function as perfumes can be referred to as ketone perfumes for convenience.

  Examples of ether compounds include anethole, eugenol, methyl eugenol, methyl isoeugenol, diphenyl oxide, 1,8-cineol, cedrylmethyl ether, ambroxane (3α, 6,6,9α-tetramethyldodecahydronaphtho [2,1- b] furan), ethoxymethylcyclododecyl ether (Boasambrenforte, manufactured by Kao Corporation), nitrogen-containing compounds such as geranyl nitrile, citronellyl nitrile, indole, acetyl cedrene, methyl anthranilate, N-methylanthranilic acid And methyl, auranthiol, and peonyl (manufactured by Dibodan). Among the ether compounds, compounds known to those skilled in the art to function as perfumes can be referred to as ether perfumes for convenience.

  (D) component of this invention is a fragrance | flavor component for flavoring objects, such as a textile product. In the present invention, a compound that has been conventionally used as a fragrance, which has been difficult to be blended as a fragrance component, and is classified as an aldehyde by the classification in the fragrance field (hereinafter sometimes referred to as (d-1) component) is blended. be able to. Therefore, the freedom degree of a fragrance | flavor preparation can be raised rather than the composition which has the conventional deodorizing effect. Therefore, in this invention, it is preferable to use an aldehyde compound as a fragrance | flavor component. When used as a fragrance, the aldehyde compound has a wide variety of fragrances and is useful from the viewpoint of perfume persistence.

  The composition of the present invention uses the deodorizing base material of the component (a) and the component (b) and the optional component (e) described later, and the pH is set to 4.0 or more and less than 6.0. There is little influence on the aldehyde fragrance in the composition system, and therefore, modulation of fragrance due to long-term storage can be suppressed, and a fresh feeling as a fragrance composition can be maintained.

[Composition of liquid fragrance composition]
The content of the phosphoric acid or salt thereof as the component (a) in the liquid flavoring agent composition of the present invention is 0.01% by mass or more, preferably from the viewpoint of deodorizing performance in terms of deodorizing performance, in terms of the acid type compound. 0.02% by mass or more, more preferably 0.04% by mass or more, and 0.9% by mass or less, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, preferably It is 0.01-0.9 mass%, More preferably, it is 0.02-0.5 mass%, More preferably, it is 0.04-0.1 mass%.

  The content of the component (b) polycarboxylic acid or its salt in the liquid flavor composition of the present invention is converted to an acid type compound, and the pH adjustment and the pH fluctuate outside the scope of the present invention. From the viewpoint of suppressing the above, 0.005% by mass or more, preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and 0.5% by mass or less, preferably 0.2% by mass or less. , More preferably 0.1% by weight or less, preferably 0.005 to 0.5% by weight, more preferably 0.01 to 0.2% by weight, still more preferably 0.02 to 0.1% by weight. It is.

  Moreover, in the liquid flavoring agent composition of this invention, the total of content of (a) component and (b) component is 0.00 from a viewpoint of the stain formation suppression at the time of using with respect to a dark-colored textile product. 02 mass% or more, preferably 0.05 mass% or more, and 1 mass% or less, preferably 0.5 mass% or less, preferably 0.02-1 mass%, more preferably 0.05- mass%. 0.5% by mass. However, the total content of the component (a) and the component (b) is, of course, selected with a content consistent with the content range or the preferable content range of the component (a) and the component (b).

  The content of the nonionic surfactant of component (c) in the liquid flavor composition of the present invention is 0. From the viewpoint of stably and sufficiently dissolving the flavor component of component (d) and imparting a fiber texture. 01% by mass or more, preferably 0.02% by mass or more, more preferably 0.04% by mass or more, and 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.3% by mass or less. Preferably, it is 0.01-1 mass%, More preferably, it is 0.02-0.5 mass%, More preferably, it is 0.04-0.3 mass%.

  Content of the fragrance | flavor component of (d) component in the liquid fragrance | flavor composition of this invention is 0.005 mass% or more for the fragrance | flavor to a textile product, Preferably it is 0.01 mass% or more. Preferably, it is 0.02% by mass or more, and for the purpose of stably dissolving the fragrance component in the composition, it is 0.5% by mass or less, preferably 0.3% by mass or less, more preferably 0.2% by mass. Or less, preferably 0.005 to 0.5 mass%, more preferably 0.01 to 0.3 mass%, still more preferably 0.02 to 0.2 mass%.

  The aldehyde compound (d-1) preferably accounts for 10% by mass or more, more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, of the component (d). The content is preferably 10 to 40% by mass, more preferably 15 to 40% by mass. By containing an aldehyde compound as a fragrance component, the degree of freedom of fragrance increases, and the fragrance sustainability of the fiber product after fragrance increases.

  In the present invention, it is known that it is used as a retention agent or diluent used in the perfume field such as dipropylene glycol, and as an antioxidant such as BHT, which is contained in the prepared perfume composition. The compound used is not counted as the content of the fragrance component of the present invention. However, what is known as a perfume ingredient that has antioxidant ability is treated as a perfume ingredient.

  The liquid flavoring agent composition of the present invention contains water. It is preferable to use water sterilized with hypochlorous acid. Water is contained in an amount such that the total amount of the liquid flavoring agent composition of the present invention is 100% by mass. Specifically, the content of water in the liquid flavoring agent composition of the present invention is preferably 80% by mass or more, more preferably 90% by mass, from the viewpoint of not deteriorating the sufficient deodorizing effect and texture to the textile product. % Or more, and preferably 99% by mass or less, more preferably 96% by mass or less.

  The pH at 25 ° C. of the liquid flavoring agent composition of the present invention is 4.0 or more, preferably 4.5 or more, in order to suppress the deodorizing effect and the scent modulation after storage, and 6 Less than 0.0, preferably less than 5.5. The pH is measured at 25 ° C. according to JIS K 3362; 2008, item 8.3.

[Other components in the composition]
In the present invention, the following components are preferably used in combination.

<(E) component: a fragrance encapsulated or immobilized in another substance>
In the present invention, as a fragrance component different from the component (d) dispersed in the composition, for example, a fragrance component as a functional component of a fine particle capsule particle including a functional component (hereinafter, encapsulated) Fragrance), and esterified products of silicic acid and a fragrance component having a hydroxy group, that is, a fragrance component as a silicate compound (hereinafter also referred to as silicate esterified fragrance), A fragrance encapsulated or immobilized in a substance can be used. WO2009 / 128549 pamphlet can be referred to as a silicic esterified fragrance. In the present invention, it is preferable that a silicate esterified fragrance is contained in the composition since the fragrance is further enhanced. Here, the silicate esterified fragrance is a compound represented by the following general formula (e1) (hereinafter may be referred to as component (e1)).

[In the formula (e1), one or more and four or less of R ^1e , R ^2e , R ^3e and R ^4e are from an alcoholic fragrance having 7 to 30 carbon atoms which may have a substituent. It is a group excluding a hydroxyl group, and the remaining group is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. ]

^Examples of the substituent that the groups R ^1e , R ^2e , R ^3e, and R ^4e in formula (e1) may have include one or more carbon atoms that may be separated by an ester bond, an amide bond, an ether bond, etc. Examples thereof include an alkyl group having 10 or less, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an acyl group having 2 to 10 carbon atoms.

In the present invention, one or more and four or less of R ^1e , R ^2e , R ^3e, and R ^4e represented by the general formula (e1) excludes a hydroxyl group from an alcoholic fragrance having 7 to 30 carbon atoms. A group obtained by removing a hydroxyl group from one or more alcoholic fragrances selected from allyl alcoholic fragrances and phenolic fragrances is more preferable.

  Allyl alcoholic fragrances are geraniol, nerol, cis-3-hexenol, trans-2-hexenol, 3-phenyl-2-propen-1-ol (cinnamic alcohol), trans-2-cis-6-nonadienal, 2 -Ethyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol (vacudanol), 2-methyl-4- (2,2,3-trimethyl-3 -Cyclopenten-1-yl) -2-buten-1-ol (sandalmysol core), 3,7,11-trimethyl-2,6,10-dodecatrien-1-ol (farnesol), 2-methyl- 5- (2,3-Dimethyltricyclo [2.2.1.02,6] hept-3-yl-2-penten-1-ol (santalol), 4-methyl-3-decen-5-ol (undecaver) Tol), 1-octen-3-ol, and allyl selected from geraniol, nerol, undecabertoal and sandalmysol core And more preferably alcohol perfume.

  Specific examples of phenolic fragrances include 4- (3-oxobutyl) phenol (raspberry ketone), eugenol, isoeugenol, 4-hydroxy-3-methoxybenzaldehyde (vanillin), 3-ethoxy-4-hydroxybenzaldehyde (ethyl vanillin) , Thymol, carvacrol, 3-methyl-4-isopropylphenol, among which raspberry ketone, vanillin and ethyl vanillin are selected because they can continuously impart a refreshing sweet scent to the fiber surface. Perfume compounds are preferred.

  The allyl alcoholic fragrance | flavor here is an alcoholic fragrance | flavor used also as a fragrance | flavor, Comprising: The alcohol compound which has a hydroxyl group in an allylic position (allylic position) refers to the compound which has an allyl group. Moreover, about a phenolic fragrance | flavor residue, the residue remove | excluding the phenolic hydroxyl group from the phenolic fragrance | flavor points out the residue remove | excluding the hydroxyl group substituted by the aromatic ring.

  The remaining group may be a group obtained by removing a hydroxyl group from alcoholic fragrances other than allyl alcoholic fragrances and phenolic fragrances. The remaining groups are groups obtained by removing hydroxyl groups from lower alcohols such as ethanol and butanol; groups obtained by removing hydroxyl groups from higher alcohols such as lauryl alcohol, myristyl alcohol, palmityl alcohol and stearyl alcohol; 2-ethylhexanol, 4 -Group which remove | excluded the hydroxyl group from Gerve alcohol, such as butyl octanol, can be mentioned.

  In this invention, it is preferable to contain the aldehyde compound (d-1) as (d) component, and the silicic-esterified fragrance | flavor (e1) as (e) component.

  In addition, since the silicate esterified fragrance of the component (e1) is added separately as a silicate ester structure unlike the component (d), the component (d) is a compound different from the fragrance component in structure. Is not included. Similarly, the encapsulated fragrance is also a compound different from the component (d) because the fragrance component in the capsule is separated from the composition of the present invention. The content of the silicate esterified fragrance as the component (e1) in the liquid fragrance composition of the present invention is preferably 0.0001 mass as the silicate ester structure, preferably in terms of fragrance persistence. % Or more, preferably 0.0005 mass% or more, more preferably 0.0008 mass% or more, and from the viewpoint of stability in an aqueous system, preferably 0.01 mass% or less, more preferably 0.00 mass%. 005% by mass or less, more preferably 0.003% by mass or less, preferably 0.0001 to 0.01% by mass, more preferably 0.0005 to 0.005% by mass, and still more preferably 0.0008 to 0%. 0.003 mass%.

<(F) Component: Amine oxide compound>
The liquid fragrance composition of the present invention comprises, as component (f), one or more compounds selected from amine oxide compounds having one or two alkyl groups or alkenyl groups having 8 to 22 carbon atoms in the molecule. It is preferable to contain. The component (f) is a preferable component from the viewpoint of further enhancing the deodorizing effect.

  The component (f) amine oxide compound preferably has one linear alkyl group or alkenyl group having 8 or more carbon atoms, 10 or more carbon atoms, 22 or less, and 18 or less carbon atoms. The alkylene oxide compound contains an organic group other than the alkyl group or alkenyl group, and the organic group has 1 to 4 carbon atoms in which one hydrogen atom of the alkyl group may be substituted with a hydroxy group. An alkyl group is mentioned. As the component (f), one or more amine oxide compounds selected from amine oxides represented by the following general formula (III) and amine oxides represented by the following general formula (IV) are preferable.

Wherein, R ¹¹ is an alkyl or alkenyl group having 8 to 22 carbon atoms, each R ¹² and R ¹³ are independently an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, R ¹⁴ Is an alkylene group having 1 to 5 carbon atoms. Y is -CONH-, -COO-, -OCO-. ]

In the amine oxide compounds of the general formula (III) and the general formula (IV), R ¹¹ is preferably an alkyl group or an alkenyl group having 8 to 18 carbon atoms, more preferably a straight chain having 10 to 18 carbon atoms. It is an alkyl group. R ¹² and R ¹³ are each independently preferably a methyl group or an ethyl group, and more preferably a methyl group. R ¹⁴ is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a propylene group. Y is preferably —CONH— or —COO—.

The component (f) is preferably a compound of the general formula (IV), more preferably a compound in which Y in the general formula (IV) is —CONH—. Furthermore, in the compound represented by the general formula (IV), Y in the general formula (IV) is —CONH—, and the total number of carbon atoms of R ¹¹ —CONH— in the general formula (IV) is 10 More preferred is a compound that is 18, such as alkylamidopropyl-N, N-dimethylamine oxide.

  The content of the amine oxide compound as the component (f) in the liquid flavoring agent composition of the present invention is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, from the viewpoint of the deodorizing effect. More preferably, it is 0.02% by mass or more, preferably 0.5% by mass or less, more preferably 0.2% by mass or less, still more preferably 0.1% by mass or less, preferably 0.005 to 0%. 0.5% by mass, more preferably 0.01-0.2% by mass, and still more preferably 0.02-0.1% by mass.

<(G) component: quaternary ammonium salt compound>
In order to enhance the deodorizing effect, the liquid flavoring agent composition of the present invention preferably contains a quaternary ammonium salt compound as the component (g). In particular, the component (g) is effective for suppressing a raw dry odor. Specifically, the group bonded to the nitrogen atom has one or two linear alkyl groups having 8 to 14 carbon atoms, preferably 8 to 12 carbon atoms, and the remaining organic group is an alkyl group. Examples thereof include a quaternary ammonium salt compound in which one of the hydrogen atoms in the group is a methyl group or an ethyl group which may be substituted with a hydroxy group, or a phenyl group, preferably a methyl group. The ammonium group and the cation constituting the salt vary depending on the alkylating agent, and preferred examples include chlorine ion, methyl sulfate ion, and ethyl sulfate ion. In the present invention, from the viewpoint of easiness of quaternization, it is preferable to use methyl chloride or dimethyl sulfate as the alkylating agent. Therefore, chlorine ion or methyl sulfate ion is preferable. The component (g) is preferably a dialkyldimethylammonium chloride salt having two alkyl groups having 8 to 12 carbon atoms.

  The content of the quaternary ammonium salt compound as the component (g) in the liquid flavor composition of the present invention is selected within a range that does not impair the effects of the present invention, and specifically, preferably 0.01% by mass. Or more, more preferably 0.05% by mass or more, and preferably 0.5% by mass or less, more preferably 0.3% by mass or less, preferably 0.01 to 0.5% by mass, more preferably Is 0.05 to 0.3 mass%, more preferably 0.05 to 0.2 mass%.

<(H) component: organic solvent>
The liquid flavoring agent composition of the present invention preferably contains an organic solvent as the component (h) in order to enhance the dissolution stability and volatility of each component.

  (H) As a component, in order to make volatilization of the liquid flavoring agent composition from the textiles after a process easy and to make it easy to dry, it is preferable to contain ethanol. As ethanol, modified ethanol can be used, and it is particularly preferable to use 8-acetylated sucrose-modified ethanol or polyoxyethylene alkyl ether sodium sulfate-modified ethanol. The content of ethanol in the liquid flavoring agent composition of the present invention is preferably 1% by mass or more, more preferably 2% by mass or more and preferably 10% by mass or less, more preferably 8% by weight or less, Is 1 to 10% by mass, more preferably 2 to 8% by mass.

  As the component (h) other than ethanol, for the purpose of phase stabilization, a lower (3 or 4 carbon) monohydric alcohol such as isopropanol, a polyhydric alcohol such as ethylene glycol, propylene glycol, glycerin or sorbitol (2 or more carbon atoms). 12 or less), diethylene glycol monoalkyl ether having an alkyl group having 1 to 4 carbon atoms, and polyethylene glycol phenyl ether having an average addition mole number of ethyleneoxy group of more than 1 and 3 or less. Examples include alkyl (poly) glyceryl ethers in which the alkyl group has 4 or less and 8 or less carbon atoms, and the average degree of condensation of glycerin is 1 or more and 3 or less. In the component (h), the proportion of ethanol is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more. (H) component is ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin, and alkyl (poly) glyceryl whose alkyl group has 4 or less and 8 or less carbon atoms, and the average degree of condensation of glycerin is 1 or more and 3 or less. It is at least one organic solvent selected from ethers, and more preferably ethanol.

[Other optional ingredients]
As a liquid fragrance | flavor composition of this invention, the following component known to be used for a deodorant and a fragrance | flavor can be contained. In that case, the agent which does not impair the pH of this invention is used.
As other components, aromatic sulfonates such as p-toluenesulfonate and m-xylenesulfonate can be blended. A nonionic surfactant other than the component (d), a cationic surfactant other than the component (g), and other surfactants may be contained. In addition, pigments, thickeners, and the like may be blended as desired, and it is preferable to blend known antiseptic / antifungal agents, bactericides, and the like.

[How to use liquid fragrance composition]
The liquid fragrance composition of the present invention can be used or used by spraying the liquid fragrance composition onto a textile product by spraying or the like, or by using a flexible material such as a fabric, nonwoven fabric or sponge. A method of wiping or rubbing a textile product by impregnating a water-absorbing substrate is mentioned. In addition, according to the present invention, there is provided a liquid fragrance article obtained by filling the liquid fragrance composition of the present invention into a container with a manual spray device.

There is no limitation in particular as a manual spray apparatus, A commercially available spray vial, a trigger type sprayer, etc. can be used. The amount of spray from the sprayer is preferably 0.01 g or more, more preferably 0.05 g or more, still more preferably 0.1 g or more, and preferably 2 for the liquid flavoring agent composition of the present invention in one stroke. 0.0 g or less, more preferably 1.5 g or less, and still more preferably 1.0 g or less, is good. As the spray vial used in the present invention, for example, a Marem spray vial can be mentioned. As the trigger type sprayer, a pressure accumulation type trigger as disclosed in Japanese Utility Model Publication No. 4-37554 is particularly suitable from the viewpoint of spray uniformity. The spray characteristics, the ground is consuming liquid area when sprayed from 15cm away in vertically spaced target object preferably 10 cm ² or more, more preferably 100 cm ² or more, more preferably 150 cm ² or more, and, preferably 800 cm ² or less, and more preferably is suitable trigger sprayer to be 600 cm ² or less. It is preferable to use a pressure-accumulating sprayer having excellent liquid dripping and spray uniformity as shown in FIG. 1 of Japanese Utility Model Laid-Open No. 4-37554.

The amount for the textiles liquid perfumed compositions of the present invention is a degree moistening when rubbing against 800 cm ² or less textile 100 cm ² or more when spraying, preferably at least 0.2 g 0. The ratio is 7 g or less.

<Perfume composition>
Perfume compositions A and B shown in Tables 1 and 2 below were prepared.
B. Antioxidant contained in perfume H. T.A. And diluent D. P. G. In the fragrance composition A, the aldehyde compound in the fragrance component is 34.1% by mass, and in the fragrance composition B, the aldehyde compound in the fragrance component is obtained. Was 12.7% by mass.

<Preparation of silicate ester>
The following compounds were synthesized as silicate esters to which perfume ingredients were added.
Silicate ester 1: Si [O-Undecav] ₄
Silicate ester 2: Si [O-Geranyl] ₄
here,
Undecav is a group obtained by removing one hydroxyl group from 4-methyl-3-decen-5-ol (undecabeltole),
Geranyl is a group obtained by removing one hydroxyl group from geraniol,
Represent each.

Synthesis Example 1 Silicate ester 1: Synthesis of Si [O-Undecav] ₄
A 500 mL four-necked flask was charged with 62.50 g (0.30 mol) of tetraethoxysilane, 183.92 g (1.08 mol) of 4-methyl-3-decen-5-ol, and 0.90 g of a 5 mass% sodium ethoxide ethanol solution, and a nitrogen stream The mixture was stirred at 123 to 150 ° C. for about 2 hours while distilling the lower ethanol. Thereafter, the pressure in the tank was gradually lowered to 18 kPa, and stirring was performed at 150 ° C. for 1 hour while distilling ethanol. Next, stirring the ethanol at a temperature of 150 ° C. for 1 hour at 8 kPa, 1 hour at 4 kPa, 2 hours at 4 kPa, and 4 hours at 2.7 kPa while distilling ethanol. Thereafter, the temperature in the tank was raised to 170 ° C. under 0.4 kPa, and 4-methyl-3-decene-5-ol remaining in the system was removed over 30 minutes. The reaction solution was cooled and filtered under reduced pressure using a membrane filter (ADVANTEC PTFE T100A090C) to obtain 176.90 g of a pale yellow oily substance 1 containing a silicate ester perfume precursor of 4-methyl-3-decen-5-ol. It was.

Synthesis Example 2 Silicate ester 2: Synthesis of Si [O-Geranyl] ₄
In a 200 mL four-necked flask, put 27.08 g (0.13 mol) of tetraethoxysilane, 72.30 g (0.47 mol) of geraniol and 0.485 mL of 2.8 mass% sodium methoxide methanol solution, and distill ethanol under a nitrogen stream to 110-120 Stir for 2 hours at ° C.
After 2 hours, the pressure in the tank was gradually lowered to 8 kPa, and the mixture was further stirred at 117 to 120 ° C. for 4 hours while distilling ethanol. Four hours later, after cooling and releasing the reduced pressure, filtration was performed to obtain 76.92 g of a yellow oily substance containing a geraniol silicate ester perfume precursor.

<Examples and Comparative Examples>
Using each component shown in Table 3, a liquid fragrance composition having the composition shown in Table 3 was prepared. The pH of the liquid fragrance composition was adjusted with 1/10 N NaOH or 1/10 N HCl. Moreover, in Table 3, the composition (mass%) of the fragrance composition is B.I. H. T.A. And D. P. G. Based on the amount excluding. B. in the composition. H. T.A. And D. P. G. Is contained, but omitted in the table and contained in the remainder of the water.
About the obtained liquid flavoring agent composition, the deodorizing effect and the remaining scented effect were evaluated by the following method. The results are shown in Table 3.

(1) Evaluation of perfume effect <Preparation of perfume object>
As a odor component, a 10 ppm ethanol solution of isovaleric acid as a sweat odor model is sprayed once onto a cotton melias cloth (10 cm × 10 cm) using a spray vial (Marem Co., No. 6) at 25 ° C. After drying for 30 minutes, a test piece was obtained. For comparison, a test piece treated in the same manner using only ethanol containing no isovaleric acid (hereinafter sometimes referred to as a comparative test piece) was also prepared.

<Deodorization method>
The test liquid containing isovaleric acid obtained by the above method and the test specimen for comparison were applied six times with a liquid perfume composition having the formulation shown in Table 3 using a spray vial (Marum Co., No. 6). Sprayed and dried at 25 ° C. for 1 hour.

<Evaluation of perfume effect>
A total of 10 specialist panelists, 5 males and 5 females in their 30s, sniff the odors of the test specimens and the test specimens for comparison, and the odors of the test specimens are evaluated using the following 6-level odor intensity display method. The average value was obtained.
0: Perfumed similarly to the test specimen for comparison.
1: I do not know what the odor is, but the strength to feel the odor that is different from the fragrance of the comparative test piece slightly (detection threshold level)
2: Easily felt weak smell (recognition threshold level), which indicates that it is the smell of isovaleric acid relative to the test specimen for comparison
3: Clear odor that feels isovaleric acid 4: Strong odor that feels isovaleric acid 5: Unsatisfactory odor, average value 0 or more and less than 1, ◎, average value 1 or more and less than 2 ○, average value 2 or more 3 Evaluation was made with less than Δ and an average value of 3 to 5 as x. The evaluation is preferably ◎ or ○.

(2) Evaluation of scent modulation after storage <Storage test>
Modulation of scent by storage was evaluated by the following method.
For the compositions in Table 3, 30 ml of the composition within 3 hours after preparation was added to the wide-mouth standard bottle PS-No. 6 and put a special lid. Separately, the same composition was prepared, and the wide-mouth standard bottle PS-No. 30 ml was put into 6 and the lid was put on, and it was stored at 40 ° C. for 20 days.
The cotton knitted fabric (size 10 cm × 10 cm) stored in a room at a temperature of 25 ° C. and a relative humidity of 60 RH% is stored with the liquid fragrance composition after storage or the liquid fragrance composition just after production. Using a trigger spray bottle on one side, the spray nozzle tip is about 10 cm away from the fabric surface, sprayed three times toward the center of the fabric, and then stored in a room at a temperature of 25 ° C and a relative humidity of 60 RH% at a temperature of 25 ° C for 24 hours. And dried. The fabric treated with the stored composition was used as an “evaluation test fabric”, and the test fabric treated with the composition immediately after preparation was used as a “comparison control fabric” to compare the incense tone after storage. Evaluation was performed according to the following evaluation criteria, based on the average of the evaluation points of five specialist panels.
・ Evaluation criteria for residual scent effect
1 : There is no scent modulation as compared with the comparative control cloth.
0 : A scent modulation is felt as compared with the comparative control cloth.
For the trigger spray bottle, the bottle part and trigger spray part of “Flare Fragrance Clothing Refresh Mist (manufactured by Kao Corporation, manufactured in January 2013)” are thoroughly washed with distilled water and ethanol and dried. It was.

・ Phosphate: Dipotassium hydrogen phosphate (mass% is mass% in terms of phosphoric acid)
・ Polyhydroxyamine: Tris (hydroxymethyl) aminomethane ・ Amine oxide: Amidopropyl laurate-N, N-dimethylamine oxide ・ Nonionic surfactant: Polyoxyethylene lauryl ether (average added mole number of ethyleneoxy group 10)
Quaternary ammonium salt compound: didecyldimethylammonium chloride Fragrance composition A: Fragrance composition described in Table 1 Fragrance composition B: Fragrance composition described in Table 2 Silicate ester 1: Synthesis Example 1 Silicate ester compound and silicate ester 2: synthesized in Example 2: Silicate ester compound synthesized in Synthesis Example 2

(3) Evaluation of modulation of scent after storage due to difference in pH Modulation of scent after storage due to difference in pH was evaluated by the following method.
[Sample preparation]
In the composition of the liquid flavoring agent composition of the present invention product 1 in Table 3, various compositions were prepared in which the pH at 25 ° C. was varied in the range of 3.0 to 8.0. As a standard for modulation of fragrance, the fragrance of the fresh mouth of the liquid fragrance composition immediately after blending is used as a reference, and the fragrance of the bottle mouth of the liquid fragrance composition after the following storage test The degree of change and deterioration in standing was discussed by three trained researchers with the ability to identify odors.
In addition, the same evaluation was performed also about the liquid fragrance | flavor composition of this invention product 9 of Table 3. In FIG.
[Preservation test]
It was stored in the same manner as the evaluation of the aftercense effect in (2) above.
[Evaluation results]
The sample after storage of any of the compositions with the pH changed based on the products 1 and 9 of the present invention has a tendency that the scent can be maintained in an acidic region, and the pH is particularly 4.0 or more and less than 6.0. For example, it was recognized that there was no scent modulation at 5.5 or lower.

Claims (4)

(A) 0.01% by mass or more and 0.9% by mass or less in terms of acid type compound when phosphoric acid or a salt thereof is converted into an acid type compound (b) a polycarboxylic acid having a molecular weight of 90 or more and 500 or less in terms of acid type compound or its 0.005% by mass or more and 0.5% by mass or less in terms of the salt converted into an acid type compound,
(C) 0.01% by mass or more and 1% by mass or less of a nonionic surfactant represented by the following general formula (I):
(D) containing 0.005 mass% or more and 0.5 mass% or less of a fragrance | flavor component, and water,
The total content of (a) and (b) is 0.02% by mass or more and 1% by mass or less,
The fragrance | flavor (d-1) which consists of an aldehyde compound is contained as (d), (d-1) occupies 10 mass% or more and 50 mass% or less among (d), and pH in 25 degreeC is 4 0.0 or more and 5.5 or less,
Liquid fragrance composition.
R ¹ —X — [(EO) _s (PO) _t ] —R ² (I)
[In Formula (I), R ¹ is an alkyl group or an alkenyl group having 10 to 22 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X is —O—. Or -COO-, EO is an ethyleneoxy group, PO is a propyleneoxy group, s and t represent the average number of added moles, t is 0 or more and 3 or less, and the sum of s + t is 5 or more 15 or less. When both (EO) and (PO) are included, (EO) and (PO) may be random addition or block addition, and there is no restriction on the order of addition. ] Further, (f) one or more compounds selected from amine oxide compounds having one or two alkyl groups or alkenyl groups having 8 to 22 carbon atoms in the molecule are 0.005% by mass to 0.5% by mass. Hereinafter, the liquid fragrance | flavor composition of Claim 1 to contain. Furthermore, (h) The liquid flavoring agent composition of Claim 1 or 2 which contains 1 to 10 mass% of ethanol. Liquid fragrance | flavor articles | goods formed by filling the liquid fragrance | flavor composition of any one of Claims 1-3 in the container with a manual spray apparatus.