JP5137672B2 - Raw dry odor control method - Google Patents

Description

  The present invention relates to a method for suppressing raw dry odor.

  When textile products such as clothes are washed and dried in the room, a so-called odor of so-called dry odor often occurs. Such an odor is considered to be caused by the action of bacteria or the like on dirt that has not been fully washed. For example, Patent Document 1 discloses a technique using an antibacterial agent as a detergent, Patent Document 2 and Patent Document 3 and the like. Is a technology that uses an antibacterial agent as a softening agent, and it is disclosed that the generation of a raw dry odor is suppressed.

Moreover, in order to deodorize the raw dry odor which generate | occur | produced, using a deodorizer is generally performed and the patent document 4 has disclosed the technique of the deodorizer containing an antibacterial agent.
JP 2006-160822 A, JP 2001-303441 A, JP 2001-303439 A JP 2001-070423 A

  The raw dry odor is caused by the fact that a gram-positive bacterium (genus Staphylococcus) decomposes dirt such as sebum and protein, and the present inventor shows that a bad odor is noticeably generated under moderate moisture and temperature conditions. These studies have revealed this. In general, when a dry odor is generated, it has been deodorized using a deodorant, but it is temporarily deodorized, but the decomposition products remain, so if the deodorizing components such as fragrances decrease, the malodor again Comes out. For this reason, it can be easily imagined that generation of a raw dry odor can be suppressed by suppressing the growth of causative bacteria. However, the act of adding additional water to the wet textile product after washing or the action of adhering a component such as a surfactant, which is a cleaning component, is not conceived by those skilled in the art or consumers. Moreover, it cannot be recalled that this kind of action can suppress the growth of bacteria very efficiently, and as a result, the generation of a raw odor can be efficiently suppressed.

  Techniques for suppressing a raw dry odor by using an antibacterial agent in a washing process detergent or softener, such as the inventions described in Patent Documents 1 to 3, are not satisfactory, although some effects are seen. In addition, the deodorant such as the invention described in Patent Document 4 is sprayed in a space where there is clothing or odor after drying, and when it is brought into contact with a wet textile product after washing / dehydration, There is no suggestion that the raw dry odor at an unprecedented high level can be suppressed.

  Accordingly, an object of the present invention is to provide a method for suppressing a raw dry odor by an unprecedented method.

  The present invention comprises (a) at least one antibacterial agent selected from cationic organic antibacterial agents, triclosan and dichlorosan, (b) at least one selected from nonionic surfactants and amine oxide type surfactants. A washing step comprising an aqueous composition containing a surfactant and water, wherein the content of the component (a) is 0.05 to 10% by mass and the content of the component (b) is 0.01 to 10% by mass. The moisture content after completion | finish of spin-drying | dehydration (ratio of the water impregnated with respect to the dry total mass of a textile product) is made to contact the textile product which is 30-120 mass%.

  According to the method of the present invention, even when the fiber product is naturally dried indoors, it is possible to effectively suppress a freshly dried odor.

[Aqueous composition]
The aqueous composition according to the present invention contains at least one antibacterial agent selected from a cationic organic antibacterial agent, triclosan and dichlorosan as the component (a).

  Examples of cationic organic antibacterial agents include quaternary ammonium salt type antibacterial agents (a1), guanidine compounds (a2), and polylysine (a3).

  Specific examples of the quaternary ammonium salt type antibacterial agent (a1) include compounds represented by the following general formula (1).

[Wherein, R ¹ represents an alkyl group having 8 to 16 carbon atoms, R ² represents an alkyl group having 8 to 14 carbon atoms or a benzyl group, and R ³ and R ⁴ each independently represent 1 to 3 carbon atoms. Represents an alkyl group or a hydroxyalkyl group, and X ⁻ represents an anion. ]
In general formula (1), R ¹ is preferably an alkyl group having 8 to 14 carbon atoms, R ² is preferably an alkyl group having 8 to 12 carbon atoms or a benzyl group, and R ³ and R ⁴ are each independently a methyl group. Is preferred. Examples of the anion represented by X ⁻ include halogen ions, sulfate ions, fatty acid ions having 1 to 12 carbon atoms, alkyl sulfate ions having 1 to 3 carbon atoms, and halogen ions are preferable.

  As the guanidine compound (a2), a biguanide antibacterial agent is preferable. Specific examples of biguanide antibacterial agents include compounds represented by the following general formula (2).

[Wherein R ⁵ represents an alkylene group having 2 to 8 carbon atoms, n represents a number of 2 to 14, and HY represents an organic acid or an inorganic acid. ]
In the general formula (2), R ⁵ is preferably an alkylene group having 4 to 8 carbon atoms, more preferably a hexamethylene group. As n, the number of 10-14 is preferable, the number of 11-13 is more preferable, and 12 is still more preferable. As HY, hydrochloric acid, gluconic acid, and acetic acid are preferable, and hydrochloric acid is more preferable.

  A commercially available compound may be used as the compound represented by the general formula (2), but it can be produced by a known method, for example, a method described in British Patent No. 702268.

As the biguanide antibacterial agent, a bis-biguanide compound can be used in addition to the compound represented by the general formula (2). Specifically, 1,2-bis- (N ⁵ -p-chlorophenyl-N ¹ -biguanide) -ethane, 1,2-bis- (N ⁵ -p-nitrophenyl-N ¹ -biguanide) -ethane, , 2-bis - (N ^{5-p-hydroxyphenyl} -N ¹ - biguanide) - ethane, 1,2-bis - (N ^{5-p-chlorobenzyl} -N ¹ - biguanide) - ethane, 1,2-bis - (N ^{5-p-bromophenyl} -N ⁵ - hexyl -N ¹ - biguanide) - ethane, 1,2-bis - (N ^{5-p-chlorophenyl} -N ^{5-2-ethylphenyl} -N ¹ - biguanide) - ethane, 1,2-bis - (N ^{5-p-chlorophenyl} -N ⁵ - ethyl -N ¹ - biguanide) - ethane, 1,2-bis - (N ^{5-p-methoxyphenyl} -N ¹ - biguanide) -Ethane and the like.

As the biguanide antibacterial agent, polyhexamethylene biguanide hydrochloride in general formula (2), wherein R ⁵ is a hexamethylene group, n is a number of 10 to 14, more preferably 11 to 13, and HY is hydrochloric acid. Salt is most preferred.

  As the component (a) of the present invention, a compound selected from guanidine compounds (a2) and polylysine (a3) is preferable from the viewpoint of the effect of suppressing a dry odor, and guanidine compounds (a2), particularly biguanide antibacterial agents, are more preferable. preferable.

  The aqueous composition according to the present invention contains at least one surfactant selected from nonionic surfactants and amine oxide surfactants as component (b).

  The nonionic surfactant has an alkyl group or alkenyl group having 8 to 20 carbon atoms, preferably an alkyl group having 10 to 14 carbon atoms, and an oxyalkylene group having 2 or 3 carbon atoms, preferably an oxyethylene group. The average 2-150 mol, preferably 3-50 mol, more preferably 5-15 mol added polyoxyalkylene alkyl or alkenyl ether (b1), the alkyl group has 8-16 carbon atoms, preferably 10-14. Examples thereof include alkyl glycosides (b2) having an average degree of condensation of 1 to 3, preferably 1 to 2, and alkylglucamides (b3) having an alkyl group having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms. As the amine oxide type surfactant, tertiary amine oxide (b4) having one alkyl group having 10 to 16 carbon atoms and two alkyl groups having 1 to 3 carbon atoms and / or two hydroxyalkyl groups, alkanoyl And tertiary amine oxide (b5) having one alkanoylaminopropyl group or alkanoyloxyethyl group having 10 to 16 carbon atoms and two alkyl and / or hydroxyalkyl groups having 1 to 3 carbon atoms. be able to.

  As the component (b), polyoxyalkylene alkyl or alkenyl ether (b1), tertiary amine oxides (b4) and (b5) are preferable, and polyoxyalkylene alkyl or alkenyl ether ( b1) and tertiary amine oxide (b4) or (b5) are preferably used in combination, and the mass ratio of (b1) / [(b4) + (b5)] is 10/1 to 1/10, more preferably 8 / It is more preferable to use so that it may become 1-1 / 8.

  The aqueous composition according to the present invention contains (a) a lower alcohol azeotroped with water as a component for the purpose of enhancing the permeability of the component (a) to the fiber product and promoting the drying of the composition. It is preferable. As a lower alcohol, C1-C3 alcohol is mentioned, Ethanol and isopropanol are preferable and ethanol is more preferable.

  The water-based composition according to the present invention is optional but has at least one compound selected from the following perfume component (d1) and the following perfume as the component (d) for the purpose of more effectively suppressing the occurrence of a raw dry odor. It is preferable to contain a fragrance composition containing at least one compound selected from the component (d2).

  Fragrance component (d1): synamic aldehyde, chabicol, hexanal, heliotropin, methyl eugenol, p-isopropylcyclohexanol, acetophenone, isoeugenol, undecanal, ethyl caproate, eugenol, octanol, carvacrol, geraniol, cyclamenaldehyde , Cedrol, terpinyl acetate, terpinene, thymol, decanol, phenylacetaldehyde, benzyl acetate, perilaldehyde, methyl salicylate, linalyl acetate, linalool, limonene, γ-undecalactone, citral, citronellal, citronellol, nerol, hinokitiol, syn Namic alcohol, l-carvone, l-menthol, terpineol, terpinene-4-o Le, camphor, borneol, anisaldehyde, vanillin, ethyl vanillin, alpha-hexyl cinnamic aldehyde, octanal, nonanal, decanal, anethole, allyl isothiocyanate.

  Perfume component (d2): dipropylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, ethylene oxide and / or propylene oxide adduct of phenolic compounds, aroma An ester compound of an aliphatic carboxylic acid and an aliphatic alcohol having 1 to 5 carbon atoms.

  In this invention, it is estimated that the fragrance | flavor component (d1) acts on the improvement of a raw-dry odor suppression effect, and the fragrance | flavor component (d2) has the effect which osmose | permeates and hold | maintains a fragrance | flavor component (d1) in a textile product.

  As the fragrance component (d1), heliotropin, eugenol, camphor, geraniol, citronellol, citral, thymol, carvacrol and limonene are preferable, and as the fragrance component (d2), dipropylene glycol is preferable. Moreover, 30 / 70-90 / 10 are preferable and, as for mass ratio (d1) / (d2) of a fragrance | flavor component (d1) and (d2), 40 / 60-80 / 20 is more preferable.

  Content of (a) component in the aqueous composition which concerns on this invention is 0.05-10 mass%, 0.05-5 mass% is preferable and 0.05-3 mass% is more preferable. (B) Content of a component is 0.01-10 mass%, 0.05-5 mass% is preferable and 0.1-3 mass% is more preferable. The component (b) is an important component for allowing the component (a) to penetrate into the fiber product, and the mass ratio of the component (a) / (b) is preferably 10/1 to 1/10. 1 to 1/10 is more preferable, and 1/1 to 1/10 is still more preferable.

  The component (c) is an important component having an effect of increasing the drying speed of the fiber product and an effect of allowing the component (a) to penetrate into the fiber product, and is preferably contained. 0.01-20 mass% is preferable, as for content of (c) component in an aqueous composition, 0.1-20 mass% is more preferable, and 1-20 mass% is still more preferable. The component (d) is also an important component that improves the effects of the present invention, and is preferably contained. The content of the component (d) in the composition is preferably 0.001 to 1% by mass, more preferably 0.001 to 0.8% by mass, and still more preferably 0.005 to 0.5% by mass. Furthermore, the component (d) is a hydrophobic substance, and is preferably dissolved, dispersed and emulsified uniformly in the aqueous composition according to the present invention. For that purpose, the mass ratio of the component (d) / (b) is 1 / 1 to 1/500 is preferable, 1/1 to 1/100 is more preferable, and 1/1 to 1/50 is still more preferable.

  The aqueous composition of the present invention is an aqueous composition obtained by dissolving, dispersing, and solubilizing the above component (a), component (b), and optionally component (c) and / or component (d) in water, As water to be used, hypochlorous acid sterilized with hypochlorous acid or the like, ion-exchanged water excluding metals present in a trace amount in water, or the like can be used. The aqueous composition of the present invention preferably contains 70 to 99.94% by mass of water.

  The pH at 25 ° C. of the aqueous composition of the present invention is preferably 7.0 to 9.5, more preferably 7.0 to 9.0, and particularly preferably 7.0 to 8. 5. In order to adjust to such 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- Organic acids such as 1,1-diphosphonic acid can be used.

[Dry odor control method]
The method for suppressing the dry odor of the present invention is a method in which the aqueous composition according to the present invention described above is brought into contact with a wet textile product that has been dehydrated in the washing step. The preferred moisture content of the wet textile product (percentage of water impregnated with respect to the total dry mass of the textile product) is 30 to 120% by mass, preferably 40 to 110% by mass, More preferably, it is 40-100 mass%. The total dry mass of the fiber product is defined as the mass of the fiber product left for 24 hours under the conditions of 25 ° C. and 65% RH.

  Examples of the method of bringing the aqueous composition according to the present invention into contact with a wet textile product include, for example, a method of filling the aqueous composition in a container equipped with a spray spraying means and spraying the textile product, a flexible product such as a sponge. Examples include a method of rubbing an aqueous composition impregnated with a functional material onto a textile product, etc. For the purpose of drawing out the effects of the present invention easily and simply, the aqueous composition is filled in a container equipped with a spraying means. Then, a method of spraying on a textile product is preferable, and a method of spraying on a wet textile product using a trigger sprayer is more preferable. At that time, the trigger sprayer has a volume average particle size of droplets of the aqueous composition after spraying of 10 to 200 μm at a point 10 cm away from the injection port in the injection direction, and droplets exceeding 200 μm It is preferable to have a spraying means so that a droplet of 1 volume% or less with respect to the total number of droplets and a volume of less than 10 μm is 1 volume% or less with respect to the total number of spray 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 type sprayer, and by using a spray nozzle having a discharge hole having a spray port diameter of 1 mm or less, preferably 0.5 mm or less. Can be easily achieved. Moreover, the shape, material, etc. of a discharge hole are not specifically limited.

  Moreover, when employ | adopting a trigger type sprayer, it is preferable from the objective of adjusting the viscosity at 20 degrees C of an aqueous composition to 15 mPa * s or less, Preferably it is 1-10 mPa * s. Such viscosity adjustment can be performed by adjusting the composition concentration, using a commercially available thickener, or the like.

  The viscosity of the aqueous 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 rotation 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 of the present invention.

In the present invention, the aqueous composition is brought into contact with the wet textile product. The amount of the aqueous composition per 0.5 m ^{2 of the} wet textile product is preferably 1.0 to 30.0 g, more preferably 3. It is 0-25.0g, Most preferably, it is 5.0-20.0g.

  After the contact, even if it is naturally dried indoors, the generation of a so-called raw dry odor is suppressed, and a very fresh but refreshing feeling can be given to the textile product.

Examples 1-5 and Comparative Examples 1-2
Using the following components (a) and (b), an aqueous composition having the formulation shown in Table 1 was prepared. As a fragrance, 5 parts by mass of ethyl cinnamate, 10 parts by mass of linalyl acetate, 5 parts by mass of linalool, 5 parts by mass of laral, 10 parts by mass of α-hexylcinnamic aldehyde, 10 parts by mass of paride, 5 parts by mass of citronellol, A blended fragrance comprising 20 parts by mass of limonene and 30 parts by mass of dipropylene glycol (mass ratio of (d1) component / (d2) component = 50/30) was used, and the resulting composition was 1N hydrochloric acid or The pH was adjusted to 8.0 (25 ° C.) with a 1/10 N aqueous sodium hydroxide solution. Moreover, the viscosity in 20 degreeC of each composition of Examples 1-5 and Comparative Examples 1-2 is in the range of 2.0-4.0 mPa * s.

  About the obtained composition, the raw dry odor suppression effect was evaluated by the following method. The results are shown in Table 1.

<Blending ingredients>
(A) Component (a-1): Didecyldimethylammonium chloride (a-2): Benzalkonium chloride (a-3): Triclosan (a-4): Polylysine (manufactured by Chisso Corporation)
(A-5): Polyhexamethylene biguanide hydrochloride (a compound manufactured by Avicia Co., Ltd., wherein R ⁵ is an alkylene group having 6 carbon atoms, n is 10, and HY is hydrochloric acid)
(B) Component (b-1): Polyoxyethylene (average number of moles of oxyethylene group added = 8) Lauryl ether (b-2): Amidopropylamine oxide (Amidated product of lauric acid and dimethylaminopropylamine) Obtained by reaction with hydrogen peroxide).

<Evaluation method of raw dry odor control effect>
(1) Preparation of the object The worn cotton underwear was washed with 20 ° C tap water at a bath ratio of 1/20 for 3 minutes, dehydrated for 1 minute, and a moisture content of 70% by mass relative to the dry clothing mass. After adjustment, the test piece was cut into 6 cm × 6 cm.

(2) Treatment method The test piece obtained by the above method was sprayed with an aqueous composition having the formulation shown in Table 1 at a mass ratio of 10% with respect to the test piece using the following sprayer. It was dried at 37 ° C./70% RH for 4 hours.

  The sprayer is a 300 ml container equipped with a Yoshino trigger sprayer (spray nozzle diameter 0.45 mm, discharge amount 0.65 mL), and these spray patterns have a volume average particle size at a point 10 cm away from the spray port in the spray direction. A droplet having a diameter of 80 to 90 μm and a droplet exceeding 200 μm is 0.5% by volume or less based on the total number of spray droplets, and a droplet less than 10 μm is 0.5 based on the total number of spray droplets. It is not more than volume%, and there is no big difference in each composition.

(3) Evaluation of raw dry odor control effect A total of 10 panelists of 5 men and 5 women in their 30s sniff the odor of the test piece, and evaluated by the following 6-step odor intensity display method, The average value was obtained. The evaluation is preferably less than 2.

0: No unpleasant odor at all 1: Strength to feel an unpleasant odor slightly (detection threshold level)
2: A weak odor that easily feels an unpleasant odor (level of recognition threshold)
3: Unpleasant odor clearly felt 4: Strong odor 5: Unbearable odor

Example 6, Comparative Example 3
A mixture containing 0.1% by mass of didecyldimethylammonium chloride as component (a), polyoxyethylene (average number of moles of oxyethylene group added = 8) lauryl ether 0.4% as component (b), and water. The mixture was stirred and adjusted to pH 8.0 (25 ° C.) with 1 N hydrochloric acid or 1/10 N aqueous sodium hydroxide solution to obtain an aqueous composition.

  This aqueous composition was processed into a textile product by the following Method 1 (Example 6) or Method 2 (Comparative Example 3), and the effect of suppressing the dry odor was evaluated in the same manner as in Example 1.

Method 1:
In the same manner as in Example 1, a test piece adjusted to a moisture content of 70% by mass with respect to the dry garment mass was obtained, and the aqueous composition was added to the test piece by mass with respect to the test piece using the above sprayer. It sprayed so that it might become 10% by ratio, and it was made to dry at 37 degreeC / 70% RH for 4 hours.

Method 2:
A test piece which was adjusted to a moisture content of 70% by mass with respect to the dry clothing mass in the same manner as in Example 1 and further dried at 37 ° C./70% RH so that the moisture content became 10% by mass. The test piece was sprayed with the above aqueous composition in the same manner and dried at 37 ° C./70% RH for 30 minutes.

  What was processed by the said method 1 had a high raw dry odor suppression effect (odor level: 1.0), but what was processed by the method 2 had a low raw dry odor suppression effect (odor level: 3.0).

Claims (4)

(A) cationic organic antibacterial agents, at least one antimicrobial agent selected from triclosan and dichloro Sun, contain (b) A Min'okishido type surfactant, and water, the content of the component (a) 0. Water content impregnated with an aqueous composition having a content of component (b) of 0.01 to 10% by mass (05% to 10% by mass) after completion of dehydration in the washing step (the amount of water impregnated with respect to the total dry mass of the textile product) The dry odor control method which makes a textile product which is 30-120 mass% contact by spraying using a trigger type sprayer . The method for suppressing dry odor according to claim 1, wherein the component (a) is an antibacterial agent selected from guanidine compounds. (B) A polyoxyalkylene alkyl or alkenyl ether (b1) having an alkyl group or alkenyl group having 8 to 20 carbon atoms and having an average of 2 to 150 moles of oxyalkylene groups having 2 or 3 carbon atoms added as a component. And a tertiary amine oxide (b4) having one alkyl group having 10 to 16 carbon atoms and two alkyl groups having 1 to 3 carbon atoms and / or two hydroxyalkyl groups as the amine oxide surfactant. A tertiary amine oxide (b5) having one alkanoylaminopropyl group or alkanoyloxyethyl group having 10 to 16 carbon atoms in the alkanoyl group and two alkyl groups and / or two hydroxyalkyl groups having 1 to 3 carbon atoms And the mass ratio of (b1) / [(b4) + (b5)] is 10/1 to 1/10, and (a) component / ( The mass-ratio of b) component is 10/1-1/10, The raw dry odor control method of Claim 1 or 2. When the trigger sprayer is used, the volume average particle size of the droplets of the aqueous composition after spraying is 10 to 200 μm at a point 10 cm away from the injection port in the injection direction, and droplets exceeding 200 μm are the total number of spray droplets. against 1 vol% or less, the droplets less than 10μm is any one of the preceding claims, in which includes a spray means such that less than 1% by volume relative to the total number of the spray droplets 3 Raw dry odor control method.