JP5809800B2 - Raw dry odor control agent - Google Patents

Description

  The present invention relates to a raw dry odor inhibitor.

  In recent years, it has been increasingly desired to remove unpleasant odors (also referred to as “unpleasant odor” in the present specification) around us due to the growing interest of consumers in the living environment. The odor adhering to textile products such as sanitary goods such as towels and bedding and clothing includes internal factors derived from the human body caused by repeated use of textile products in addition to external factors such as tobacco.

Underwear, towels, handkerchiefs and other textiles that come into direct contact with human skin, or textiles that may absorb or adhere to sebum-containing sweat or skin, When left in a humid place such as a washing tub for a while, when drying indoors, when wet with rain or sweat, or when drying is insufficient, a specific odor may be generated. This odor is generally called a raw dry odor, and most can be removed by sufficient drying. However, even if the fiber product is sufficiently dried and no longer feels a dry odor, if the fiber product is damp due to sweat or rain, a rag-like raw dry odor may be generated. Once the fiber product generates this raw dry odor, the dry odor can be temporarily removed by sufficient drying after washing, but the raw dry odor like a dust cloth tends to recur during use. Such a dry-dry odor that is likely to recur may occur not only when drying indoors, but also when using a washing machine or dryer equipped with a low-temperature drying function, or even when drying outdoors, even when humid. is there.
A characteristic feature of a recurrent raw dry odor is that it does not occur after washing and is sufficiently dried, or is almost reduced, but odor is generated only by being damp. A recurrent raw dry odor is likely to occur when stored in a chiffon for a long time. However, textile products that are frequently used with human skin, such as underwear, handkerchiefs, or towels, and that are frequently used for a short period of the cleaning-use cycle, will smell during use once this dry-dry odor has been generated. Often recurs. Furthermore, the odor intensity of a freshly dried odor tends to increase as the number of washings increases.

  By the way, several types of fatty acids including 4-methyl-3-hexenoic acid have been proposed so far as an indicator substance for a raw dry odor (see Patent Document 1). 4-Methyl-3-hexenoic acid is naturally known as a component of eggplant (see Non-Patent Document 1), and is also known to be produced by microorganisms from terpenes (see Patent Document 2). However, in these documents, there is no description or suggestion about the mechanism of generation of a raw dry odor. In addition, it does not disclose the relationship between several kinds of fatty acids including 4-methyl-3-hexenoic acid and a recurrent dry odor.

On the other hand, as a method for removing off-flavors and the like generated from textile products, masking using a fragrance component and antibacterial or antibacterial sterilization of microorganisms that cause off-flavor using antibacterial agents are known.
As a masking method using a fragrance component, a masking method using a fabric treatment agent containing an alicyclic ketone compound as a fragrance component or a stabilizer of a fragrance component is known (for example, see Patent Documents 3 and 4). ). Known methods of deodorization by antibacterial and sterilization of microorganisms that cause off-flavors include methods using diketone compounds, cationic organic antibacterial agents, treatment agents containing fungicides such as triclosan and dichlorosan, etc. Yes. For example, Patent Literature 5 discloses a technique for suppressing a raw dry odor using a bactericide. Patent Document 6 discloses a technique for suppressing a non-microbial malodor by using a diketone compound to suppress a malodor associated with sweating. In addition, Patent Document 7 discloses a surfactant and a fragrance selected from terpene hydrocarbons, aliphatic alcohols and cyclic ketones for masking and stabilizing the fragrance of the liquid bleach containing hydrogen peroxide. A liquid bleach composition containing is disclosed.

JP 2009-244094 A JP 56-124387 A JP 2010-31285 A JP 2007-314693 A JP 2009-263812 A JP-A-4-202122 JP 2005-239770 A

53rd Symposium on Fragrance, Terpene and Essential Oil Chemistry Abstracts of Society (2009) p. 4-6

  The present invention provides a raw dry odor inhibitor having excellent ability to suppress a raw dry odor generated from a textile product, in particular, a repetitive raw dry odor caused by wetting (wetting moisture) after the textile product is dried. The task is to do. Moreover, this invention makes it a subject to provide the method for suppressing a raw dry odor which suppresses a raw dry odor efficiently.

In view of the above problems, the present inventors have conducted extensive studies from the viewpoints of causative substances, causative bacteria, and generation mechanisms of raw dry odors. As a result, new knowledge was obtained. That is, as a causative substance of a raw dry odor, intermediate branched fatty acids such as 4-methyl-3-hexanoic acid, 4-methyl-3-hexenoic acid, 5-methyl-2-hexenoic acid, and 5-methyl-2-hexenoic acid are used. It was known that, among these, the threshold value of 4-methyl-3-hexenoic acid was particularly low compared with other substances, and it was found to be the main causative substance. Furthermore, among the fresh-dry odors, recurring raw-dry odors that rebound by being dampened after the textiles are sufficiently dried are those that have certain microorganisms removed even after they have been sufficiently removed after drying. It was found that the odor was produced by growing or growing in the fiber product, or the odor that was trapped in the fiber by drying was released again by the wetting of the fiber product, and it was easy to feel because it was a low threshold. . And it discovered that recurrent re-dried odor was the intermediate | middle branched fatty-acid odor which mainly has the said 4-methyl-3- hexenoic acid.
Furthermore, further examination was performed based on such knowledge. As a result, it has been found that a carbonyl compound having a specific structure is useful for suppressing a dry odor. Furthermore, it has been found that such a carbonyl compound suppresses the production of 4-methyl-3-hexenoic acid, which is a main causative substance of a raw dry odor, by microorganisms.
The present invention has been completed based on these findings.

  That is, the present invention relates to a raw dry odor suppressor comprising a compound represented by the following general formula (1).

(In the formula, R ¹ is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or —O—R ³ (R ³ is an alkyl group having 1 to 5 carbon atoms or 2 to 5 carbon atoms) A broken line indicates that a double bond may be present, and R ² represents an alkyl having 1 to 5 carbon atoms bonded to a carbon atom constituting the ring. A group or an oxo group, provided that when R ² is an oxo group, R ² is double-bonded to the carbon atom on the ring to which R ¹ is bonded via the carbonyl carbon, where n is 1. And an aromatic hydrocarbon group is removed from the alicyclic hydrocarbon group in the general formula (1), and the total carbon number of the compound represented by the general formula (1) is 10 to 10. 16)
Moreover, this invention relates to the raw-dry odor suppression composition containing the said raw-dry odor inhibitor.

Furthermore, the present invention relates to a 4-methyl-3-hexenoic acid production inhibitor comprising the compound represented by the general formula (1).
The present invention also relates to a 4-methyl-3-hexenoic acid production inhibitor composition containing the 4-methyl-3-hexenoic acid production inhibitor.

  Furthermore, the present invention brings the raw dry odor inhibitor or raw dry odor suppressor composition or the 4-methyl-3-hexenoic acid production inhibitor or the 4-methyl-3-hexenoic acid production inhibitor composition into contact with a textile product, The present invention relates to a method for suppressing raw dry odor, which suppresses generation of a raw dry odor from the textile product.

  The raw dry odor suppressant of the present invention has an excellent ability to suppress a raw dry odor generated from a textile product, particularly a repetitive raw dry odor caused by wetting after drying. Moreover, according to the raw dry odor control method of this invention, a raw dry odor can be suppressed efficiently.

The raw dry odor inhibitor and 4-methyl-3-hexenoic acid (also referred to as 4M3H in this specification) production inhibitor of the present invention are composed of a carbonyl compound represented by the general formula (1).
In general, the mechanism of action of odor control agents such as raw dry odor is to sterilize microorganisms adhering to textile products, prevent conversion to raw dry causative substances such as sweat and sebum remaining on textile products, Examples include decomposition or conversion into odorless substances and masking of raw odors. In addition, the mechanism of action of the “raw dry odor inhibitor” in the present invention is to prevent the sebum soil component from being converted to 4M3H, which is one of the raw dry odor causing substances, and suppress the production of 4M3H.
As shown below, cis / trans isomers exist in 4M3H, and in the present invention, both cis-type and trans-type compounds are included.

  In the present specification, “sebum dirt” is the most typical dirt that adheres to textile products such as clothing, and contains a large amount of oils such as free fatty acids and glycerides. What is trapped in mud, exfoliated keratin, etc. is observed in textile products. The “sebum stain component” is not particularly limited as long as it is a component of sebum stain usually found in clothing and the like, but a substance that can be a precursor of a raw dry odor-causing substance generated from a textile product is preferable. As a substance that can be a precursor of a raw dry odor-causing substance generated from a textile product, for example, a saturated or unsaturated anteiso fatty acid having 9 to 21 carbon atoms (preferably 11 to 19 carbon atoms, more preferably 17 to 19 carbon atoms) ( 6-methyloctanoic acid, 8-methyldecanoic acid, 12-methyltetradecanoic acid, 14-methylhexadecanoic acid, 16-methyloctadecanoic acid, 14-methylhexadecenoic acid and 16-methyloctadecenoic acid), and salts and esters thereof Is mentioned. Among these are compounds that are not actually present in sebum soil.

In general, the term “raw dry odor” refers to an odor that is generated when a used fiber product is washed and dried, or when the fiber product is wet. However, even if the dry odor can be temporarily removed by sufficiently drying the textile, it can be used immediately after drying or after storage, or after using the textile for a while, or after rain, sweat, etc. The wet odor like a rag-like odor may reappear from textile products due to moisture, etc. In this specification, the odor-like raw dry odor that recurs when the textile product from which the raw dry odor has been temporarily removed by sufficiently drying is dampened in this specification is referred to as “recurrent raw dry odor” or “recurrent Sometimes called odor.
Raw dry odors that occur due to insufficient drying after washing textile products include complex odors such as S (sulfur) odor, N (nitrogen) odor, aldehyde odor, lower fatty acid odor, and intermediate branched fatty acid odor including 4M3H odor. . On the other hand, after removing the dry odor by sufficiently drying the textile product, the recurrent unpleasant odor of the rag-like odor recurring from the textile product again due to moisture such as rain, sweat, etc. is an intermediate class mainly 4M3H odor Branched fatty acid odor is the majority, and other highly volatile odors such as S odor, N odor, and aldehyde odor hardly occur.
Moreover, “raw dry odor suppression” includes suppressing raw dry odor and preventing raw dry odor production. In the present invention, the recurrent raw dry odor, particularly the suppression of 4M3H odor, is characteristically indicated as the raw dry odor.

  The carbonyl compound represented by the following general formula (1) used in the present invention will be described in detail.

In General Formula (1), R ¹ is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or —O—R ³ (R ³ is an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms. A alkenyl group of ˜5). A broken line indicates that it may be a double bond. R < ² > shows a C1-C5 alkyl group or oxo group couple | bonded with the carbon atom which comprises the ring. However, when R ² is an oxo group, R ² is double-bonded at the γ position with respect to the carbon atom on the ring to which R ¹ is bonded via the carbonyl carbon. n shows the integer of 1-3. The aromatic hydrocarbon group is excluded from the alicyclic hydrocarbon group in the general formula (1). Moreover, the total carbon number of the compound represented by General formula (1) is 10-16.

In the general formula (1), specific examples of the alicyclic hydrocarbon group include a cyclohexyl group, a cyclohexenyl group, and a cyclohexadienyl group. However, the aromatic hydrocarbon group is excluded from the alicyclic hydrocarbon group in the general formula (1). Hereinafter, in the present specification, conditions excluding the aromatic hydrocarbon group may be omitted.
In the general formula (1), when the alicyclic hydrocarbon group is a cyclohexadienyl group, the double bond of the ring is preferably conjugated. Of course, two double bonds indicated by broken lines are not adjacent to each other with one carbon atom in the ring (also referred to as cyclo).

In General Formula (1), R ¹ is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or —O—R ³ (R ³ is an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms. A alkenyl group of ˜5).
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ¹ or R ³ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl, tert-butyl, and n-pentyl group. , Tert-pentyl group and the like.
Examples of the alkenyl group having 2 to 5 carbon atoms represented by R ¹ or R ³ include vinyl group, 1-propenyl group, 2-propenyl group, 3-butenyl group, 1-pentenyl group, 3-pentenyl group and 4-pentenyl. Groups.
In general formula (1), R ¹ is preferably an alkyl group having 2 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a group represented by —O—R ³ , an ethyl group, 1- A propenyl group, a 3-butenyl group, and an ethoxy group are preferable. R ³ is preferably an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms.

In the general formula (1), R ² is attached to a carbon atom constituting the ring, an alkyl group or an oxo group having 1 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms represented by R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl, tert-butyl, n-pentyl group, tert- A pentyl group etc. are mentioned. In the present invention, R ² is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-pentyl group or an oxo group, and more preferably a methyl group. When there are a plurality of R ^{2 s} , they may be the same or different.

When R ² is an alkyl group having 1 to 5 carbon atoms, at least one R ² is bonded to the α-position and / or β-position with respect to the carbon atom on the ring to which R ¹ is bonded via the carbonyl carbon. It is preferable. For example, two alkyl groups may be bonded to the α-position with respect to the carbon atom on the ring to which R ¹ is bonded via the carbonyl carbon. Further, when two alkyl groups are bonded to one carbon atom on the ring, the alkyl group is preferably a methyl group.

When R ² is an oxo group, R ² is double bonded to the γ position relative to the carbon atom on the ring to which R ¹ is bonded via the carbonyl carbon. In the general formula (1), when R ¹ oxo group at position γ with respect to the carbon atom on the ring bonded through a carbonyl carbon is a double bond, R ¹ is attached via a carbonyl carbon ring It is preferable that an alkyl group having 1 to 6 carbon atoms such as a methyl group (preferably a methyl group) is bonded to the above carbon atom at the α-position.

In General formula (1), n shows the integer of 1-3 and 2 or 3 is preferable. When n is 2 or 3, a plurality of R ² may be bonded to one carbon atom constituting the ring of the alicyclic hydrocarbon group in the compound represented by the general formula (1), or alicyclic You may couple | bond with the different carbon atom which comprises the ring of a hydrocarbon group. Alternatively, the ring structure of the alicyclic hydrocarbon group may include a carbon atom having a plurality of substituents and a carbon atom having one substituent.

  In this invention, the total carbon number of the compound represented by General formula (1) is 10-16, 12-15 are preferable and 13 is more preferable.

  Although the specific example of a compound represented by General formula (1) below is shown, this invention is not limited to these.

Among the compounds exemplified as the compound represented by the general formula (1),
Exemplary compound (1) (1- (2,6,6-trimethyl-2-cyclohexen-1-yl) -2-buten-1-one, α-damascone),
Exemplary compound (2) (1- (2,6,6-trimethyl-1-cyclohexen-1-yl) -2-buten-1-one, β-damascone),
Exemplary compound (3) (1- (2,6,6-trimethyl-3-cyclohexen-1-yl) -2-buten-1-one, δ-damascone),
Exemplary compound (4) (1- (2,6,6-trimethyl-1,3-cyclohexadien-1-yl) -2-buten-1-one, β-damasenone),
Exemplary compound (5) (1- (3,3-dimethyl-6-cyclohexen-1-yl) -pent-4-en-1-one, α-DYNASCONE),
Exemplary compound (6) (1- (3,3-dimethyl-1-cyclohexen-1-yl) -pent-4-en-1-one, β-DYNASCONE),
Exemplary compound (7) (ethyl 2,2,6-trimethyl-cyclohexane-1-carboxylate, THESARONE),
Illustrative compound (8) (ethyl 2,6,6-trimethyl-cyclohexa-1,3-diene-1-carboxylate, ethyl safranate (ETHYL SAFRANATE)),
Exemplary Compound (11) (1- (p-Menten-6-yl) -1-propanone, NERONE)
Exemplary compound (12) (1- (2,4,4-trimethyl-2-cyclohexen-1-yl) -2-buten-1-one, isodamascone),
Exemplary compound (13) (ethyl 2-methyl-4-oxo-6-pentylcyclohex-2-ene-1-carboxylate, Calyxol),
Exemplary compound (14) (ethyl 2-ethyl-6,6-dimethylcyclohex-2-ene-1-carboxylate, divescon (GIVESCONE)),
Illustrative compound (15) (methyl 2,2-dimethyl-6-methylene-1-cyclohexane-1-carboxylate, ROMASSCONE), and illustrative compound (16) (2,6,6-trimethyl-1,3 -Cyclohexene-1-carboxylic acid-2-propen-1-yl)
Is more preferable.

In the present invention, a commercially available compound may be used as the compound represented by the general formula (1). For example, the compound represented by the general formula (1) includes Givaudan SA, IFF (International Flavors and Fragrances), Firmenich SA, Symrise AG, Takasago International Corporation, Kao Can be purchased as a fragrance material or reagent from Sigma-Aldrich, Quest, etc.
Moreover, the compound represented by General formula (1) can also be synthesize | combined by a normal manufacturing method. For example, the exemplary compound (16) can be synthesized by reacting the exemplary compound (8) with allyl alcohol to perform a transesterification reaction and removing the generated ethanol.

  In the present invention, the composition may contain the raw dry odor suppressor or 4M3H production inhibitor. In these compositions, only one type of compound represented by the general formula (1) may be contained, or two or more types of compounds represented by the general formula (1) may be contained.

In the composition of the present invention, the compound represented by the general formula (1) is preferably used after being solubilized or emulsified in a solvent or dispersion medium (in this specification, the solvent or dispersion medium is referred to as “solvent”). .
As the solvent used for solubilization or emulsification of the compound represented by the general formula (1), a low boiling point solvent removed from the fiber product by drying is preferable, and a solvent having a boiling point of 110 ° C. or less at 1013 hPa is more preferable. A solvent having a boiling point of 105 ° C. or lower at 1013 hPa is particularly preferable. Suitable solvents include water; lower alcohols such as methanol, ethanol, propanol and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; hydrocarbon solvents such as hexane and toluene; acetonitrile and the like.

  The density | concentration of the compound represented by General formula (1) in the composition of this invention can be suitably determined with the solvent to be used, the base material to be used together, and / or a use.

  In the composition of the present invention, the compound represented by the general formula (1) may be solubilized or emulsified in a solvent using a solubilizer. There is no restriction | limiting in particular as a solubilizer, The solvent which has affinity to both water and oil is preferable. Specifically, lower alcohols such as methanol, ethanol, propanol, and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; mono- or dialkyl ethers having 1 to 4 carbon atoms of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and ethylene glycol , C1-C4 mono or dialkyl ether of propylene glycol, C1-C4 mono or dialkyl ether of diethylene glycol (preferably diethylene glycol monobutyl ether), C1-C4 mono or dialkyl ether of dipropylene glycol, etc. These glycol solvents are mentioned. Such a solubilizer is preferably used in such an amount that the compound represented by the general formula (1) can be uniformly solubilized or emulsified in a solvent such as water. The solubilizer is contained in the liquid in an amount of 0.01 to 50% by mass, more preferably 0.01 to 10% by mass, further preferably 0.01 to 5% by mass, and particularly preferably 0.1 to 3% by mass. preferable.

In the composition of the present invention, the compound represented by the general formula (1) may be solubilized or emulsified in a solvent using a surfactant. There is no restriction | limiting in particular as surfactant, Specifically, C10-C15 alkylbenzenesulfonic acid or its salt, C8-C16 alkyl sulfate ester salt, C2 or C2 of an alkyleneoxy group is C2 or C3. Yes Anionic surfactants such as polyoxyalkylene alkyl ether sulfates having an average addition mole number of alkyleneoxy groups of 0.2 to 6 and an alkyl group of 8 to 16 carbon atoms, average addition of alkyleneoxy groups Polyoxyalkylene alkyl ether having a mole number of 0.2 to 6 and an alkyl group having 8 to 16 carbon atoms, an alkyl glycoside having an alkyl group having 8 to 16 carbon atoms and an average degree of glucose condensation of 1 to 2 Nonionic surfactants such as alkyltrimethylammonium salts having an alkyl group of 8 to 18 carbon atoms and dials having a total carbon number of 16 to 36 Cationic surfactants such as Le trimethyl ammonium salts.
The content of the surfactant in the composition of the present invention is preferably 1 ppm or more, and more preferably 2 ppm or more. Moreover, when it contains 500 ppm or more of surfactant, it is preferable to contain 0.2 ppm or more of compounds represented by General formula (1).

  The raw dry odor inhibitor and 4M3H production inhibitor of the present invention may contain a fragrance. The fragrance that can be used in the present invention is not particularly limited, but hydrocarbon fragrance, alcohol fragrance, ether fragrance, aldehyde fragrance, ketone fragrance, ester fragrance, lactone fragrance, cyclic ketone fragrance, etc. Ordinary fragrances can be used. 0.01-10 mass% is preferable, as for content of the fragrance | flavor component in the raw dry odor inhibitor and 4M3H production | generation inhibitor of this invention, 0.01-5.0 mass% is more preferable, 0.02-1.0 Mass% is particularly preferred.

  The pH of the composition of the present invention at 25 ° C. is preferably 7.0 to 9.5, more preferably 7.0 to 9.0, and particularly preferably 7.0 to 8.5, from the viewpoint of the effect of suppressing the dry odor. preferable. To adjust to pH, alkali agents such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, citric acid, ethylenediaminetetraacetic acid, 1-hydroxyethyl-1,1 -Organic acids such as diphosphonic acid can be used.

  You may mix | blend hydrotrope agents, such as paratoluenesulfonic acid salt, xylenesulfonic acid, and cumenesulfonic acid salt, with the composition of this invention.

  The density | concentration of each component in the composition of this invention can be suitably adjusted with the intended use use, a processing method, etc., and the mixture ratio of each component can be adjusted with the target fragrance etc.

The method for suppressing raw dry odor of the present invention comprises bringing the raw dry odor suppressor or 4M3H formation inhibitor of the present invention, or the raw dry odor suppressing composition or 4M3H composition comprising the same into contact with a textile product, and then subjecting the textile product to raw drying. Suppresses the generation of odors.
There is no restriction | limiting in particular as a raw material of the textiles in this invention, Any of natural materials, such as wool, silk, and cotton, chemical fibers, such as polyester and polyamide, and these combination may be sufficient. In the present invention, the material of the textile product is preferably cotton. The fiber product may be unused or used once or more. The raw dry odor inhibitor or 4M3H formation inhibitor of the present invention, or the textile product brought into contact with the raw dry odor suppressor composition or 4M3H composition containing the same may contain moisture / moisture, and may be sufficiently dried. It may have been done.

  For expression of the effect of the present invention, the dry-dry odor inhibitor of the present invention or the 4M3H production inhibitor, It is preferable to bring the raw dry odor suppressing composition or the 4M3H composition comprising this into contact with the textile product. Moreover, it is preferable to contact so that the texture of a textile product etc. is not affected, 1 g or less is more preferable, and 100 mg or less is especially preferable.

Although there is no restriction | limiting in particular as a method of making the raw dry odor inhibitor or 4M3H production | generation inhibitor of this invention, or the raw dry odor suppression composition or this containing 4M3H composition contact a textiles, For example, the composition of this invention A method of impregnating a fiber product into a fiber, a method of spraying a fiber product after filling the composition of the present invention into a container equipped with a spraying means, a fiber of the composition of the present invention impregnated with a flexible material such as sponge The method of rubbing on the product can be mentioned. For the purpose of drawing out the effects of the present invention sufficiently for simplicity and convenience, there are a method of filling the composition of the present invention in a container equipped with a spraying means and spraying the fiber product, and a method of impregnating the fiber product into the composition of the present invention. preferable.
In the case of performing the spray treatment, the spray means is preferably a sprayer, and examples thereof include aerosol, mist, or a trigger type pump type. When a pump type sprayer is used, it is preferable to use a so-called pressure accumulation type that causes little dropout. In the present invention, a method of spraying a textile product using a trigger sprayer is more preferable.

  When the composition of the present invention is actually used, for example, when the composition of the present invention is sprayed onto a textile product using a trigger sprayer, the composition is sufficient to uniformly adhere to the textile product. It is necessary to spray things. In addition, when impregnating a fiber product into the composition of the present invention, taking into account that the active ingredient is lost due to dehydration or rinsing after the impregnation, the base used in the composition of the present invention is sufficient for the fiber product. Need to remain in quantity.

When spraying on a textile product using a trigger sprayer, the volume average particle diameter of the droplets of the composition after spraying is 10 to 200 μm at a point 10 cm away from the injection port in the injection direction, and a liquid exceeding 200 μm It is preferable to have a spraying means in which droplets are 1% by volume or less with respect to the total number of sprayed droplets, and droplets with less than 10 μm are 1% by volume or less with respect to the total number of sprayed droplets. Such a particle size distribution can be measured by, for example, a laser diffraction particle size distribution meter (manufactured by JEOL Ltd.). As a method for controlling the spray particle size, it is preferable to use a manual trigger sprayer, and the spray port diameter is preferably 1 mm or less, more preferably 0.5 mm or less. This can easily be achieved. Moreover, the shape, material, etc. of a discharge hole are not specifically limited.
When spraying on textiles using a trigger sprayer, the viscosity of the composition at 20 ° C. is preferably 15 mPa · s or less, and more preferably 1 to 10 mPa · s. The viscosity of the composition can be adjusted by adjusting the composition concentration or using a commercially available thickener. The viscosity of the composition of the present invention is measured as follows. First, the rotor number no. Prepare one equipped with one rotor. The sample is filled in a tall beaker and prepared at 20 ° C. in a constant temperature bath at 20 ° C. A sample prepared at a constant temperature is set in a viscometer. The rotational speed of the rotor is set to 60 rpm, and the viscosity 60 seconds after the start of rotation is taken as the viscosity of the aqueous composition.

When the composition of the present invention is sprayed on the fiber product using a trigger sprayer or the like, the spray amount of the composition of the present invention per 400 cm ^{2 of} the fiber product is preferably 0.1 to 3.0 g, 0.2 -2.0g is more preferable, and 0.5-1.0g is especially preferable. Further, the spray amount of the compound represented by the general formula (1) is preferably 0.02 to 50 mg, more preferably 0.1 to 20 mg, particularly preferably 0.2 to 10 mg per 400 cm ² of the textile product. When spraying on a textile product using a trigger sprayer, the content of the compound represented by the general formula (1) is not particularly limited unless the effect of the odor on the product is considered. 1 ppm to 1000 ppm is preferable in the composition because there is a concern that the degree of freedom in the design of the fragrance is reduced.
When the fiber product is impregnated into the composition of the present invention, the amount of impregnation of the composition with respect to the fiber product is preferably fiber product / composition = 1/1 to 1/30, and 1/2 to 1/20 in mass ratio. More preferred is 1/3 to 1/10. The temperature of the composition when impregnated is preferably 5 to 40 ° C, more preferably 10 to 35 ° C. The impregnation time is preferably 1 to 30 minutes, more preferably about 5 to 15 minutes. The composition of the present invention preferably contains 1 to 10,000 ppm of the compound represented by the general formula (1). Further, the textile product may be impregnated with the textile product itself, or the textile product may be impregnated with a diluted solution obtained by diluting the concentrated solution composition with tap water or the like.

In the present invention, there is no particular limitation on the detection and quantification method of 4M3H. However, 4M3H exists in a mixed state with many other organic substances in the textile products actually used in human life. Moreover, while the threshold value of 4M3H is very low, the threshold value and the detection intensity differ depending on the type of coexisting organic substance. Therefore, for example, 4M3H can be measured by the following method. However, the present invention is not limited to this.
About 50 g of textile products such as clothing are cut, extracted with 500 mL of dichloromethane, and concentrated under reduced pressure. Further, 200 mL of 1M aqueous sodium hydroxide solution is added to the extraction solution, and 200 mL of 2M hydrochloric acid is added to the recovered aqueous layer to make it acidic. To this solution, 200 mL of dichloromethane is added, the organic layer is concentrated under reduced pressure, and the concentrated acidic component is made up to 1 mL.
Subsequently, using a gas chromatograph manufactured by Agilent connected to a preparative fraction collector (PFC) manufactured by GUSTER, the concentrate was fractionated by GC retention time under the following conditions, and 30 GCs around the target component were 6 mm in inner diameter. , And collected in 200 mg of TENAX TA (trade name, manufactured by GL Sciences Inc.) filled in a glass tube having a length of 117 mm.
The gas chromatography conditions are shown below.
(GC-PFC conditions)
GC: Agilent 6890N (trade name, manufactured by Agilent)
Column: DB-1 (trade name, manufactured by Agilent), length 30 m, inner diameter 0.53 mm, film thickness 1 μm
40 ° C. for 1 min. hold → 6 ° C./min. to 60 ° C. → 4 ° C./min. to 300 ℃
Injection volume: 2μL
PFC (manufactured by Gerstel): trap time 18 min. to 24 min., 30 times
trap: Tenax TA (trade name, manufactured by GL Sciences Inc.) 200 mg

As shown in the examples described later, a raw dry odor is an odor produced by a specific microorganism that survives or grows in a textile product, or an odor that is trapped in the fiber by drying is a wetness of the textile product. It was released again and found that it was easy to feel because of the low threshold. Then, it was found that the recurring raw dry odor is an intermediate branched fatty acid odor mainly composed of 4M3H. Furthermore, it discovered that the raw dry odor inhibitor and 4M3H production | generation inhibitor of this invention suppressed the production | generation by the microorganisms of 4M3H which are the main causative substances of raw dry odor, and suppressed raw dry odor. Therefore, according to the present invention, the object of the present invention can be achieved without sterilizing the causative bacteria of the generation of a raw dry odor, and a sufficient effect can be obtained without relying on masking with a fragrance. However, the composition of the present invention does not deny the blending of bactericides and fragrances, and may contain these.
The microorganisms having 4M3H capability of producing the bacteria causing half-dried odor, Moraxella (Moraxella) bacteria, Acinetobacter (Acinetobacter) bacteria, shade MONAS (Pseudomonas) bacteria, Bacillus (Bacillus) bacteria, Sphingomonas (Sphingomonas) bacteria belonging to the genus Ralstonia (Ralstonia) bacteria belonging to the genus, queue pre-Avi Das (Cupriavidus) bacteria belonging to the genus, cyclo Enterobacter (Psychorobacter) bacteria belonging to the genus Serratia (Serratia) bacteria belonging to the genus Escherichia (Escherichia) bacteria, Staphylococcus (Staphylococcus) bacteria belonging to the genus , Burkholderia bacteria, Saccaromyces yeasts, Rhodotorula yeasts, and the like. Specifically, Moraxella sp (Moraxella sp.), Moraxella Osuroenshisu (Moraxella osloensis), Acinetobacter Radio Regis Tense (Acinetobacter radioresistens), Acinetobacter Junii (Acinetobacter JuNii), Acinetobacter calcoaceticus (Acinetobacter calcoaceticus ), Serratia marcescens (Serratia marcescens), Escherichia Korai (Escherichia coli), Staphylococcus aureus (Staphylococcus aureus), Pseudomonas Alcaligenes (Pseudomonas alcaligenes), Bacillus cereus (Bacillus cereus), Bacillus subtilis (Bacillus subtilis), cyclo Arthrobacter Pasi Fi forsythensis (Psychrobacter pacificensis), cyclo Arthrobacter Gurashinkora (Psychrobacter glacincola), Sphingomonas Yanoi Yae (Sphingomonas yanoikuyae), Ralstonia sp (Ralstonia sp.), Saccharomyces cerevisiae (Saccaromyces cerevisiae), Rhodotorula Mushiraginosa (Rhodotorula mucilaginosa), Rhodotorula Surufie (Rhodotorula slooffiae), queue pre-Avi Das oxa Ratih dregs (Cupriavidus oxalaticus) And Burkholderia cepacia .

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to this.

Test Example 1 Identification of causative substance of raw dry odor A cotton towel having a strong raw dry odor after washing and drying was collected from a household, cut into 50 g, extracted from 500 mL of dichloromethane, and concentrated under reduced pressure. Furthermore, 200 mL of 1M sodium hydroxide aqueous solution was added to the extraction solution, the aqueous layer was recovered, and 200 mL of 2M hydrochloric acid was added to make it acidic. To this solution, 200 mL of dichloromethane was added, the organic layer was concentrated under reduced pressure, and the acidic component concentrate was made up to 1 mL.

Subsequently, using a gas chromatograph manufactured by Agilent with a Gestel Preparative Fraction Collector (PFC) device connected, the concentrate was fractionated by the GC retention time under the following conditions, and the GC around the target component was divided into 30 batches. It was collected in 200 mg of a filler (trade name: TENAX TA, manufactured by GL Sciences) filled in a glass tube having an inner diameter of 6 mm and a length of 117 mm.
(GC-PFC conditions)
GC: Agilent 6890N (trade name, manufactured by Agilent)
Column: DB-1 (trade name, manufactured by Agilent), length 30 m, inner diameter 0.53 mm, film thickness 1 μm
40 ° C. for 1 min. hold → 6 ° C / min. to 60 ° C. → 4 ° C./min. to 300 ℃
Injection volume: 2μL
PFC (manufactured by Gerstel): trap time 18 min. to 24min., 30times
trap: TENAX TA (trade name, manufactured by GL Sciences Inc.) 200mg

Finally, the target component collected in TENAX was analyzed under the following conditions with a device in which a Thermal Desorption system (TDS) manufactured by GUSTER Co. was connected to GC-MS manufactured by Agilent.
(TDS-GC-MS conditions)
GC: Agilent 6890N (trade name, manufactured by Agilent)
MS: Agilent 5973 (trade name, manufactured by Agilent)
TDS desorption conditions: 250 ° C., purge flow rate 50 mL / min, purge time 3 min.
Column: DB-FFAP (trade name, manufactured by Agilent), length 30 m, inner diameter 250 μm, film thickness 0.25 μm
40 ° C. for 1 min. hold → 6 ° C / min. to 60 ° C. → 2 ° C./min. to 240 ℃

  As a result of the analysis, it became clear that the main cause substance of raw dry odor was intermediate branched fatty acid odor including 4M3H.

Test Example 2 Identification of causative bacterium causing dry odor (1) Isolation of strain After washing and drying, a cotton towel or bath towel that had ran dry odor was cut, and LP diluent (manufactured by Nippon Pharmaceutical Co., Ltd.) was added and stirred. A 0.1 ml solution was smeared on a lecithin-polysorbate-added soybean casein digest (also referred to herein as SCD-LP) agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.), cultured at 35 ° C. for 24 hours, and then obtained colonies Microorganisms were isolated from. The isolated bacterial strain is identified by determining the base sequence of about 500 bp upstream of the 16S rDNA gene, and the yeast strain is identified by determining the base sequence of the approximately 200-500 bp region of the D2 region of LSU. And based on the identity. The identity of the base sequence was calculated using the gene information processing software CustalW. Moraxella sp. Was identified by determining the base sequence of Moraxella osloensis ATCC 19976 and comparing it with that base sequence.
The strains isolated from each towel or bath towel are shown in Table 1.

(2) Raw dry odor reproduction test on textile products Each strain isolated above was inoculated into a cotton towel that had a raw dry odor, or a cotton towel that had been sterilized after washing after use. After culturing at 35 ° C for 24 hours in a humidified condition (humidity 100%), an agreement was made by a professional evaluator (N = 3) who was trained in perfume evaluation based on the following criteria for the occurrence of a fresh odor. Judged by.
1: Generation of a raw dry odor is very strong 2: Generation of a raw dry odor is strong 3: Generation of a raw dry odor is weak 4: No raw dry odor is generated The results are shown in Table 1.

From the results in Table 1, Moraxella sp. Was isolated from all freshly dried odor generating towels and bath towels. The isolated Moraxella sp. Also had a large number of bacteria. Furthermore, when the isolated Moraxella sp. Was inoculated into a sterilized towel with a fresh odor, it was confirmed that a very strong fresh odor was generated.
Therefore, it was clarified that specific microorganisms such as this species are involved in the raw dry odor.

Test Example 3 Selection of Microorganisms Capable of Generating 4M3H Soybean / Casein Digest (also referred to as SCD in the present specification) agar by a standard method from the strain and environment (soil, house) isolated and identified according to Test Example 2 After separation using a medium or a PDA medium, the 4M3H production ability of the strains isolated and identified and the microorganisms obtained from the microorganism depository were measured.
The strains obtained from the microorganism depository are as follows.

Moraxella Osloensis NCIMB10693 strain (purchased from NCIMB (National Collection of industrial and marine bacteria))
Moraxella Oslo Ensis ATCC19976 (purchased from ATCC (American Type Culture Collection))
Cyclo Arthrobacter Inmobirisu (Psychrobacter immobilis) NBRC15733 share, cyclo Arthrobacter Pasi Fi forsythensis NBRC103191 share, cyclo Arthrobacter Gurashinkora NBRC101053 strain, Pseudomonas aeruginosa (Pseudomonas aeruginosa) NBRC13275 strain, Pseudomonas putida (Pseudomonas putida) NBRC14164 share, Sphingomonas Yanoikuyae NBRC15102, Micrococcus luteus NBRC3333, Brevundimonas diminuta NBRC12697, Roseomonas aerilata NBRC106435, Cupriavidas oxalaticas 593 sp (Pseudoxanthomonas sp.) NBRC101033 strain, Serratia marcescens NBRC12648 share, Enterobacter cloacae (Enterobacter cloacae) NBRC3320 shares, Korinebakuteri -Time efficiens (Corynebacterium efficiens) NBRC100395 strain, Escherichia Korai NBRC3972 strain, Staphylococcus aureus NBRC13276 strain, Saccharomyces cerevisiae NBRC1661 strain, Candida albicans (Candida albicans) NBRC1061 shares, Arugarigenesu faecalis (Alcaligenes faecalis) NBRC13111 shares, Burkholderia cepacia NBRC15124 and Rhodotorula mushiraginosa NBRC0909 (both purchased from NITE Biological Resource Center)
Bacillus cereus JCM2152 strain, Bacillus subtilis JCM1465 strain and Lactobacillus plantarum JCM1149 strain (purchased from JCM (Japan Collection of Microorganisms))

Further, for Moraxella bacteria, the identity of the base sequence of the 16S rDNA gene region with the base sequence shown in SEQ ID NO: 1, SEQ ID NO: 2 or SEQ ID NO: 3 was determined. The base sequences shown in SEQ ID NO: 1, SEQ ID NO: 2 or SEQ ID NO: 3 are the bases of the 16S rDNA gene region of Moraxella sp. 4-1 strain, Moraxella sp. 4-4 strain and Moraxella osloensis ATCC 19976 strain, respectively. Indicates the sequence. Furthermore, the identity of the base sequence was calculated using genetic information processing software CustalW (http://clustalw.ddbj.nig.ac.jp/top-j.html). Moraxella Sp. 4-1 shares were commissioned on October 14, 2010 to the National Institute of Advanced Industrial Science and Technology Patent Biological Depositary Center (1-1-1 Tsukuba Center Central, Tsukuba City, Ibaraki Prefecture). Deposited under the number FERM P-22030.
The results are shown in Table 2.

1. Selection using used textile products One platinum loop of the obtained strain was inoculated into 5 mL of SCD liquid medium (manufactured by Nippon Pharmaceutical Co., Ltd.) and cultured with shaking (160 rpm) at 35 ° C. for 24 hours. The cultured cells are centrifuged (8000 × g, 10 minutes) to remove the supernatant, suspended in 5 mL of physiological saline, centrifuged again (8000 × g, 10 minutes), the supernatant is removed, and the physiological A bacterial solution was prepared using saline so that OD ₆₀₀ = 1.0.
A used cotton towel that has been used and washed in daily life is cut into a 5cm x 5cm square and sterilized, and 0.1 mL of the various bacterial solutions are inoculated and allowed to stand at 37 ° C for 24 hours under humidified conditions. I put it.
An expert evaluator (N = 3) determined by agreement whether or not the cotton used towels had been left for 24 hours had a dry odor. The evaluation criteria were ◎ for a sample that felt a strong odor, ◯ for a sample that felt a odor, Δ for a sample that felt a little odor, and x for a sample that did not have any odor at all. The results are shown in Table 3.

2. Selection using fiber product coated with sebum stain component According to JP 2009-149546 A, 14-methylhexadecanoic acid was synthesized by the following two-step reaction.
(A) Step 12-dodecanolide 11.9 g (60.0 mmol), 32% hydrogen bromide / acetic acid solution 24.3 g (96.0 mmol, 1.6 eq) were added to a Teflon-protected 100 mL autoclave. The mixture was purged with nitrogen, sealed, and stirred with a magnetic stirrer for 16 hours using an oil bath at 60 ° C. After cooling, 14 mL of water was added, and the mixture was transferred to a separatory funnel using 200 mL of hot hexane. After washing with ion-exchanged water, drying with magnesium sulfate, filtration, and crystallization with n-hexane gave 14.4 g (yield 86%) of 12-bromododecanoic acid.
Step (b) Next, to a 100 mL four-necked flask equipped with a reflux condenser, a 50 mL dropping funnel, a magnetic stirrer, and a temperature sensor, 5.0 g (17.9 mmol) of 12-bromododecanoic acid and triphenylphosphine (Kanto) 28.2 mg (0.006 eq) was added and dried under reduced pressure. Under an argon atmosphere, 77.1 mg (0.03 equivalent) of copper (I) bromide (Aldrich) and 10 mL of anhydrous tetrahydrofuran were added. At room temperature, 39.5 mL (3 equivalents, 1.36N tetrahydrofuran solution) of 2-methylbutylmagnesium bromide was added dropwise over 1 hour. After stirring for 1 hour, 50 mL of 1N aqueous hydrochloric acid was added, and the mixture was extracted twice with 100 mL of hexane. After washing twice with 50 mL of ion exchange water, it was dried over magnesium sulfate. Filtration and concentration under reduced pressure gave 3.9 g of a crude product.
Gas chromatography (column: manufactured by Agilent, trade name: Ultra-2, 30 m × 0.2 mm × 0.33 μm, DET 300 ° C., INJ 300 ° C., column temperature 100 ° C. → 300 ° C., 10 ° C./min) As a result of quantification using octadecane, the yield was 79%.
In this way, 14-methylhexadecanoic acid was obtained from 12-dodecanolide in a total yield of 68%. The purity was 98%.

  16-methyloctadecanoic acid was replaced with 15-pentadodecanolide in step (a) of the 14-methylhexadecanoic acid synthesis step shown above, and 2-methylbutylmagnesium bromide in step (b). Was replaced by sec-butylmagnesium bromide in the same manner, and 16-methyloctadecanoic acid was obtained from 15-pentadodecanolide in a total yield of 84%. The purity was 95%.

Each strain was inoculated into 5 mL of SCD liquid medium (manufactured by Nippon Pharmaceutical Co., Ltd.), and cultured with shaking (160 rpm) at 35 ° C. for 24 hours. The cultured cells are centrifuged (8000 × g, 10 minutes) to remove the supernatant, suspended in 5 mL of physiological saline, centrifuged again (8000 × g, 10 minutes), the supernatant is removed, and the physiological A bacterial solution was prepared using saline so that OD ₆₀₀ = 1.0.
Apply a solution of 0.5 mg of 14-methylhexadecanoic acid or 16-methyloctadecanoic acid synthesized by the above-mentioned method as a sebum stain component to a plain weave cloth of cotton cut into 2 cm x 2 cm squares in 0.1 mL of methanol. Then, methanol was dried up.
The above-mentioned cotton plain weave cloth was inoculated with 0.1 mL of the various bacterial solutions and allowed to stand at 37 ° C. for 24 hours under humidified conditions, and the following 4M3H determination and sensory evaluation of the live-dry odor were performed.

(1) Quantification of 4M3H 10 mL of methanol was added to the towel after standing for 24 hours, 1 mL of which was mixed with 1 mL of ADAM (9-Anthdiadiamethane, manufactured by Funakoshi, 0.1 w / v%), and room temperature And left for 60 minutes for derivatization.
Thereafter, about 10 μL solution, LC-FL (liquid chromatography device: HITACHI ELITE LaChrom (trade name, manufactured by Hitachi), column: Lichlorosphere 100 RP-8 (e) (trade name, manufactured by Agilent, 5 μm × 125 mm × 4 mmφ) ), Column temperature: 40 ° C., eluent: acetonitrile / water = 7/3 (volume ratio) mixed solution, flow rate: 1.0 mL / min, detector: excitation wavelength (365 nm), measurement wavelength (412 nm)) The generated 4M3H was quantified by using the analysis. Regarding the amount of 4M3H produced, the sample in which the amount of 4M3H produced was greater than 1 μg, ◎ the sample greater than 0.1 μg and 1 μg or less, ◯ the sample greater than 0 μg and 0.1 μg or less, and the sample not detected at all Was evaluated as x. Table 4 shows the results when 14-methylhexadecanoic acid was applied, and Table 5 shows the results when 16-methyloctadecanoic acid was applied.
(2) Sensory evaluation of raw dry odor The expert evaluator (N = 3) determined the presence or absence of the raw dry odor of the cotton plain weave fabric after standing for 24 hours. The evaluation criteria were ◎ for a sample that felt a strong odor, ◯ for a sample that felt a odor, Δ for a sample that felt a little odor, and x for a sample that did not have any odor at all. Table 4 shows the results when 14-methylhexadecanoic acid was applied, and Table 5 shows the results when 16-methyloctadecanoic acid was applied.

  From the results of Tables 3, 4 and 5, among various microorganisms, among the various microorganisms, Moraxella bacteria, Acinetobacter bacteria, Pseudomonas bacteria, Bacillus bacteria, Sphingomonas bacteria, Cupriavidas bacteria, Ralstonia bacteria, Cyclobacter It can be seen that specific microorganisms such as genus bacteria, Serratia bacteria, Escherichia bacteria, Staphylococcus bacteria, Burkholderia bacteria, Saccharomyces yeasts, Rhodotorula yeasts and the like have 4M3H producing ability. Furthermore, it has been clarified that such a microorganism having 4M3H generating ability is involved in the generation of a raw dry odor.

Example 1
A SCD-LP agar medium (manufactured by Wako Pure Chemical Industries, Ltd.) was inoculated with Moraxella sp. Strain 4-1 as a test bacterium and cultured at room temperature for 1 to 2 weeks to prepare a preculture plate. The surface of the colony was scraped from the preculture plate with congeal, suspended in 5 mL of physiological saline, and adjusted to OD ₆₀₀ = 1.0 (about 10 ⁸ CFU / mL).

  A cotton knitted fabric (color dyeing company, cotton knitted fabric, non-silquette processed) that has been sterilized and dried to a constant state at 25 ° C. and 40% RH is cut into 2 cm × 2 cm squares and used as a sebum stain component as described above. A solution prepared by dissolving 0.5 mg of 14-methylhexadecanoic acid synthesized in 1 in 0.1 mL of methanol was applied. Thereafter, methanol was dried to prepare a model test cloth.

  A methanol solution of the compound shown in Table 6 below (obtained as a reagent from Tokyo Kasei Kogyo Co., Ltd. or as a fragrance material from Filmenich or Kao Co., Ltd.) was prepared. The methanol solution was applied to the model test cloth at 20 ° C. so as to be 1 μg, dried at room temperature for 2 hours, and then dried to methanol. 0.1 mL of the bacterial suspension was applied to the model test cloth, and cultured in a petri dish at 37 ° C. and a relative humidity of 70% for 24 hours to prepare a bacterial fixing cloth.

  Sensory evaluation of the model test cloth was performed by a professional evaluator who can sniff out the raw odor. The evaluation criteria were evaluated as ◯ for those having a raw dry odor suppressing effect, △ for those that were difficult to judge or those having a weak raw dry odor suppressing effect, and × for those having no raw dry odor suppressing effect. The results are shown in Table 6.

  From the results shown in Table 6, a clear effect of suppressing the dry odor was observed in β-damasenone which is a compound represented by the general formula (1).

Example 2
Instead of the compounds shown in Table 6, a bacterial fixing cloth was prepared in the same manner as in Example 1 except that the amount of the compound applied to 1 g of the model test cloth was changed to 10 μg using the compounds shown in Table 7. In the same manner as in Test Example 3, the amount of 4M3H in the bacteria-fixed cloth was quantified, the ratio to the amount of 4M3H produced when no compound was added was calculated, and the 4M3H production inhibition rate was measured. The results are shown in Table 7.

The exemplified compounds and the comparative compounds (C-1) and (C-2) were obtained as reagents or fragrance materials from Firmenig, Takasago Fragrance, Inc., Quest, Gibodan, or Tokyo Chemical Industry.
Comparative compound (C-3) was synthesized as follows. In a 25 mL three-necked flask, 7.77 g of ethyl 2,2,6-trimethylcyclohexa-1,3-diene-1-carboxylate, 6.13 g of 1-hexanol and 5% sodium ethoxide (ethanol solution) 56g was added and it stirred at 140-145 degreeC under nitrogen flow for about 2 hours. After 2 hours, the pressure in the tank was 40 kPa, and stirring was continued for about 11 hours. After cooling for 11 hours, hexane was added and the mixture was transferred to a 200 mL separatory funnel and washed twice with 50 mL of saturated brine and three times with 50 mL of ion-exchanged water. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further distilled under reduced pressure (70 to 90 Pa, bath temperature 110 to 130 ° C.), whereby 7.65 g of comparative compound (C-3) (2,2,2 6-Trimethylcyclohexa-1,3-dienecarboxylic acid hexyl) was obtained as a colorless oil (yield 76%).

  As is clear from Table 7, the 4M3H production effect is not observed in the comparative compound, whereas the 4M3H production inhibitor of the present invention has an excellent 4M3H production effect.

Example 3
Example 1 except that the compound shown in Table 8 was used instead of the compound shown in Table 6 and the amount of the compound applied to 1 g of the model test cloth was 0.01 μg, 0.1 μg, 1 μg, or 10 μg. Prepare a bacterial colonization cloth in the same manner as above, and 5 expert evaluators set the odorless to 0, and when not treated with the inhibitor test substance (blank), set the raw dry odor intensity to 5, and applied each compound to dry. Odor intensity was evaluated. The results are shown in Table 8.

  As can be seen from Table 8, the comparative compound does not have the effect of suppressing the dry odor, whereas the raw dry odor inhibitor of the present invention has an excellent effect of suppressing the dry odor.

Example 4
Of the underwear of adult men in their 20s to 40s who repeated washing and use multiple times, underwear (100% cotton) that does not smell when dry, but emits a dry odor of the same odor when damp. A piece that was cut into 5 cm × 5 cm and confirmed by a professional evaluator as having the same odor level was used as an actual clothing test cloth. In addition, when qualitatively analyzing the raw odor of the same odor, it was confirmed to be a middle-branched fatty acid odor mainly having a 4M3H odor.
The actual clothing test cloth was thoroughly washed and immediately left in an environment of 25 ° C. and a relative humidity of 35% for 24 hours to be sufficiently dried. The odor intensity | strength of the actual clothing test cloth after drying confirmed that it was the below-mentioned evaluation criteria 1 by the same expert evaluator.
Next, Compositions 1 to 6 having the compositions shown in Table 9 were put in a commercially available polyethylene spray container and sprayed with 0.05 g per one piece of the above-mentioned actual clothing test cloth.
The following odor intensity evaluation tests (odor intensity evaluations A to C) were performed on the actual clothing test cloths thus prepared.

<Odor intensity evaluation A (evaluation of recurrent dry odor generated from fiber products in the dry state)>
The actual clothing test cloth sprayed with the compositions 1 to 6 was stored for 24 hours in an incubator with a relative humidity of 70% at 37 ° C. in an environment where a raw dry odor is likely to occur. The sensory evaluation of raw dry odors (complex odors including intermediate branched fatty acid odors such as S odor, N odor, aldehyde odor, lower fatty acid odor, 4M3H odor) was conducted by five expert evaluators on the actual clothing test cloth after storage. .
<Odor intensity evaluation B (evaluation of recurrent raw dry odor generated from dry textile products)>
The actual clothing test cloth subjected to the odor intensity evaluation A was left to stand in an environment of 25 ° C. and a relative humidity of 35% for 24 hours to dry the actual clothing test cloth sufficiently. Sensory evaluation of raw odor (complex odor including intermediate-branched fatty acid odors such as S odor, N odor, aldehyde odor, lower fatty acid odor, 4M3H odor) is performed on the actual clothing test cloth after drying by five expert evaluators. It was.
<Odor strength evaluation C (evaluation of recurrent dry odor generated by rewetting the textile product)>
The actual clothing test cloth used in the odor intensity evaluation B was sprayed with 0.1 g of tap water using a spray container. Immediately after the tap water was sprayed, the actual clothing test cloth wetted again was subjected to sensory evaluation of a recurrent raw dry odor (intermediate branched fatty acid odor mainly consisting of 4M3H odor) by five expert evaluators.

The evaluation results of the odor intensity evaluations A to C were determined by agreement of professional evaluators based on the following evaluation criteria.

(Evaluation criteria)
1: No odor at all 2: Almost no odor 3: Somehow odors 4: Some odors that can be understood by sniffing 5: All odors clearly understood

The results of the odor intensity evaluations A to C are shown in Table 9.

As is clear from the results in Table 9, compositions 5 and 6 of the comparative examples did not show any effect of suppressing the raw dry odor generated from the raw fiber product (odor intensity evaluation A). Here, in the odor intensity evaluation A, the raw dry odor generated from the fiber product sprayed with the compositions 5 and 6 was a composite odor containing a 4M3H odor. In addition, it is common that odor intensity | strength will fall if textiles are fully dried, and also when using the composition 5 and 6 of a comparative example, the odor intensity | strength of the freshly dried odor generated from the textile product in a dry state is temporary. (Odor intensity evaluation B). However, when the completely dried fiber product was wetted again, the fiber product sprayed with the compositions 5 and 6 of the comparative example reappeared as an intermediate dry fatty acid odor such as 4M3H odor as the main odor (odor) Strength evaluation C).
On the other hand, it can be seen that the composition of the present invention has an excellent effect of suppressing fresh and dry recurrent odors. Specifically, even in the freshly dried state, the freshly dried odor, which is a complex odor containing intermediate-branched fatty acid odors, was suppressed in the textiles brought into contact with the compositions 1 to 4 of the present invention (odor intensity evaluation A). Furthermore, even when the fiber product that has been completely dried is re-moistened, the intermediate branched fatty acid odor mainly consisting of 4M3H odor is predominant in the fiber product contacted with the compositions 1 to 4 of the present invention. Recurrent raw dry odor was suppressed (odor intensity evaluation C).

Example 5
The undergarment cut to 5 cm × 5 cm as in Example 4 having the same odor level was used as an actual clothing test cloth. Compositions 7 to 9 having the compositions shown in Table 10 were diluted 1000 times with tap water at 20 ° C., and the actual clothing test cloth was impregnated with the diluted solution at a mass ratio of 1/8 for 10 minutes. Then, after sufficiently drying the actual clothing test cloth without placing it in an environment where a raw odor is likely to be generated, 0.1 g of tap water was sprayed onto the actual clothing test cloth using a spray container to moisten the actual cloth. The clothing test cloth was placed in a square sterilized petri dish with a lid and allowed to stand at 25 ° C. for 12 hours. Then, the sensory evaluation of the repetitive raw dry odor (intermediate branched fatty acid odor mainly consisting of 4M3H odor) was performed on the wet garment test cloth by five expert evaluators. As a result, the compositions 7 to 9 of the present invention had an excellent recurring raw dry odor suppressing effect without causing odor. On the other hand, when treated with water without using the composition of the present invention, the conventional odor was confirmed, and the recurring raw dry odor suppressing effect was not confirmed.

Claims (8)

Below made of general formula (1) one of the compounds represented by two or more, for inhibiting the production of 4-methyl-3-hexenoic acid by a microorganism having the 4-methyl-3-hexenoic acid producing ability Agent .

(In the formula, R ¹ is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or —O—R ³ (R ³ is an alkyl group having 1 to 5 carbon atoms or 2 to 5 carbon atoms) A broken line indicates that a double bond may be present, and R ² represents an alkyl having 1 to 5 carbon atoms bonded to a carbon atom constituting the ring. A group or an oxo group, provided that when R ² is an oxo group, R ² is double-bonded to the carbon atom on the ring to which R ¹ is bonded via the carbonyl carbon, where n is 1. And an aromatic hydrocarbon group is removed from the alicyclic hydrocarbon group in the general formula (1), and the total carbon number of the compound represented by the general formula (1) is 10 to 10. 16) To the carbon atoms on the ring to which R ¹ is bonded via the carbonyl carbon, the α-position and / or β-position, an alkyl group represented by R ² are attached one or more of claim 1, wherein the 4-methyl An agent for suppressing the formation of -3-hexenoic acid. The compound of the general formula (1) is 1- (2,6,6-trimethyl-2-cyclohexen-1-yl) -2-buten-1-one (α-damascone), 1- (2,6, 6-trimethyl-1-cyclohexen-1-yl) -2-buten-1-one (β-damascone), 1- (2,6,6-trimethyl-3-cyclohexen-1-yl) -2-butene- 1-one (δ-damascon), 1- (2,6,6-trimethyl-1,3-cyclohexadien-1-yl) -2-buten-1-one (β-damacenone), 1- (3, 3-dimethyl-6-cyclohexen-1-yl) -pent-4-en-1-one (α-dynascon), 1- (3,3-dimethyl-1-cyclohexen-1-yl) -pent-4- En-1-one (β-dynascon), 2,2,6-trimethyl-cyclohexane-1-carboxylic acid ethyl (thesalon), 2,6,6-trimethyl-cyclohexa-1,3-diene-1-carboxylic acid Ethyl (ethyl sufuranate), 1- (p-menten-6-yl) -1-propanone (Neron), 1- (2,4,4-Trimethyl Ru-2-cyclohexen-1-yl) -2-buten-1-one (isodamacenone), ethyl 2-methyl-4-oxo-6-pentylcyclohex-2-ene-1-carboxylate (Calyxol), 2 -Ethyl-6,6-dimethylcyclohex-2-ene-1-carboxylate (divescon), methyl 2,2-dimethyl-6-methylene-1-cyclohexane-1-carboxylate (lomascone) and 2,6 The production of 4-methyl-3-hexenoic acid according to claim 1 or 2 , which is selected from the group consisting of 2,6-trimethyl-1,3-cyclohexen-1-carboxylic acid-2-propen-1-yl agent for. The compound of the general formula (1) is 1- (2,6,6-trimethyl-2-cyclohexen-1-yl) -2-buten-1-one (α-damascone), 1- (2,6, 6-trimethyl-1-cyclohexen-1-yl) -2-buten-1-one (β-damascone), 1- (2,6,6-trimethyl-3-cyclohexen-1-yl) -2-butene- 1-one (δ-damascon), 1- (2,6,6-trimethyl-1,3-cyclohexadien-1-yl) -2-buten-1-one (β-damasenone), 2,2,6 -Ethyl trimethyl-cyclohexane-1-carboxylate (thesalon), ethyl 2,6,6-trimethyl-cyclohexa-1,3-diene-1-carboxylate (ethyl safranate), 1- (2,4,4- Consists of trimethyl-2-cyclohexen-1-yl) -2-buten-1-one (isodamacenone) and ethyl 2-methyl-4-oxo-6-pentylcyclohex-2-ene-1-carboxylate (Calyxol) The 4-methyl-3-hexe according to claim 3, which is selected from the group. Agent for suppressing acid production. The microorganisms capable of producing 4-methyl-3-hexenoic acid are Moraxella sp., Moraxella osloensis , Acinetobacter radioresistens , Acinetobacter junii ( Acinetobacter junii) ), Acinetobacter calcoaceticus ( Acinetobacter calcoaceticus ), Serratia marcescens , Escherichia coli , Staphylococcus aureus , Pseudomonas ceres (Bacillus cereus), Bacillus subtilis (Bacillus subtilis), cyclo Arthrobacter Pasi Fi forsythensis (Psychrobacter pacificensis), cyclo Arthrobacter Gurashinkora (Psyc hrobacter glacincola), Sphingomonas Yanoikuyae (Sphingomonas yanoikuyae), Rusutonia sp (Ralstonia sp.), Saccharomyces cerevisiae (Saccaromyces cerevisiae), Rhodotorula Mushiraginosa (Rhodotorula mucilaginosa), Rhodotorula Surufie (Rhodotorula slooffiae), queue pre-Avi Das The production of 4-methyl-3-hexenoic acid according to any one of claims 1 to 4 , which is selected from the group consisting of SP ( Cupriavidus sp.) And Burkholderia cepacia. agent for. The microorganisms capable of producing 4-methyl-3-hexenoic acid are Moraxella sp., Moraxella osloensis , Acinetobacter calcoaceticus , Pseudomonas alcaligenes), Bacillus cereus (Bacillus cereus), cyclo Arthrobacter Pasi Fi forsythensis (Psychrobacter pacificensis), Sphingomonas Yanoikuyae (Sphingomonas yanoikuyae), Rusutonia sp (Ralstonia sp.), Saccharomyces cerevisiae (Saccaromyces cerevisiae), Rhodotorula Mushiraginosa ( Rhodotorula mucilaginosa), Rhodotorula Surufie (Rhodotorula slooffiae), and is selected from the group consisting of Burkholderia cepacia (Burkholderia cepacia), according to claim 5 - agents for inhibiting the production of methyl-3-hexenoic acid. Containing agent for inhibiting the production of claims 1 to 6, according to any one of the 4-methyl-3-hexenoic acid, 4-methyl-3-hexenoic acid composition for suppressing the generation. The composition for suppressing the production of 4-methyl-3-hexenoic acid according to claim 7 , which suppresses the production of 4-methyl-3-hexenoic acid in a textile product.