JP2012061121A - Aqueous gel aromatizer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous gel aromatizer using a perfume containing a fixed amount or more of a perfume material having logP of 4-6, which is obtained by absorbing a perfume aqueous solution in which the perfume containing the fixed amount or more of the perfume material having logP of 4-6 is stably dissolved in large quantity, and which is excellent in retaining performance of a liquid component.SOLUTION: The aqueous gel aromatizer contains: (a) a specific anionic surfactant represented by general formula (a1) HO-[(CHO)/(CHO)]-H; (b) a specific amine oxide compound; (c) a perfume containing 30-100 mass% of a perfume material having logP of 1-6 and 10-80 mass% of a perfume material having logP of 4-6; (d) a water absorptive resin; and water, in which the mass ratio of (a)/(b) is 5/95 to 55/45.

Description

  The present invention relates to an aqueous gel fragrance.

  Air fresheners that use aqueous gel (hereinafter sometimes referred to as aqueous gel air fresheners) are widely used in stationary air fresheners because they do not have to worry about liquid spilling out of the container and are superior in design. . In particular, an aqueous gel fragrance prepared by absorbing a solution in which a fragrance component such as a fragrance is dispersed in a powdered or spherical water-absorbing resin (hereinafter also referred to as the water-absorbing resin) has a large gel surface area. Therefore, the volatilization of the fragrance component is promoted, and it is a very excellent form that it can be filled with a sufficiently strong fragrance even in a wide space

  At this time, a powdery or spherical water-absorbing resin that absorbs water in which a fragrance component such as a fragrance is dispersed, emulsified or dissolved (hereinafter referred to as a fragrance-containing liquid mixture) is a water-absorbent resin prepared by crosslinking a hydrophilic polymer. It is. The water-absorbing resin used in the aqueous gel fragrance includes a water-absorbing resin containing nonionic polyalkylene oxide, a water-absorbing resin containing isobutylene-maleic anhydride copolymer, and a water-absorbing resin containing polyacrylic acid (salt). And a water-absorbing resin containing an acrylamide-acrylic acid (salt) copolymer.

  With respect to the aqueous gel fragrance prepared by absorbing a fragrance-containing liquid mixture in a cross-linkable absorbent resin, studies are being made on the design properties and water absorption of the aqueous gel. Patent Documents 1 and 2 describe hydrogels containing surfactants such as polyoxyethylene alkyl ether and polyoxyethylene hydrogenated castor oil ether. Patent Document 3 describes an aqueous gel fragrance containing an amine oxide and a fragrance in a specific ratio.

JP 2007-291145 A JP 2007-291146 A JP 2010-162327 A

  In recent years, with the diversification of user preferences, there is an increasing demand for various products with different fragrances for fragrances. On the other hand, there is an increasing demand for scent sustainability as a function required for fragrances. In order to increase the persistence of the fragrance, there are methods such as using a fragrance material having a low vapor pressure, or using a material having a low fragrance performance as a fragrance but having a low vapor pressure as a retention agent. However, in a solubilized system using a surfactant in an aqueous system, the behavior differs from the vapor pressure of the fragrance material alone. Many fragrance materials with log P of 1 to 4 are easily dissolved in water, and Henry's law is established when molecules are dissolved in water. Therefore, especially in a dilute system, the fragrance material in an aqueous solution is more than the vapor pressure of the fragrance material alone. The vapor pressure is low. Moreover, although the fragrance | flavor raw material whose log P is 4-6 tends to be low in water solubility, even if the vapor pressure value alone is high in the water solubilization system by the surfactant, the interaction with the surfactant does not occur. Vapor pressure decreases with strength. That is, the fragrance material having log P of 1 to 6 tends to have a lower vapor pressure value in the solubilized system than in the single system, and the order is different from the case of the single system in the order of water or the surface activity used for solubilization. It depends on the strength of the interaction with the agent. Therefore, the fragrance | flavor raw material whose logP is 1-6 can become a component which raises the persistence of fragrance in the aqueous system or the system solubilized in water by surfactant even if the vapor pressure value in a single system is high. On the other hand, fragrance materials having a log P in the range of more than 6 have a strong interaction with the surfactant but are difficult to solubilize, and there are few variations in fragrance. Therefore, in a solubilized system using an aqueous surfactant, a fragrance material having a log P of 1 to 6 makes it easy to achieve both fragrance variation and fragrance maintenance, and is suitable for preparing various fragrance fragrances. It is. The absolute amount of the fragrance blending amount is also important for maintaining the fragrance sustainability. However, in particular, perfume materials with a log P of 4 or more often have low solubility in water, and in aqueous systems, they can be used to some extent with surfactants and hydrotropes. The amount that can be made cannot be improved sufficiently. Since a perfume material that is insufficiently solubilized is difficult to be absorbed by an aqueous gel, in order to obtain an aqueous gel-type fragrance that can maintain both a fragrance variation and a fragrance blended in a large amount, the log P is 4 or more. There arises a problem that a perfume aqueous solution in which a large amount of the perfume material is stably solubilized must be obtained. In addition, the aqueous gel-like fragrance compounded with a fragrance material having a low vapor pressure in an aqueous system or a solubilized system with a log P of 1 to 6 has a high scent persistence, but the water evaporates over time, so that As a result, it has been found that there is a problem that liquid components other than water are separated from the water-absorbent resin, and the liquid looks smeared. It has been found that the techniques of Patent Documents 1 to 3 are insufficient to solve the above problems.

  An object of the present invention is to produce a fragrance aqueous solution in which a large amount of a fragrance containing a certain amount of a fragrance material having a log P of 4 to 6 is stably solubilized, to obtain an aqueous gel fragrance that absorbs the fragrance, and log P Is to provide an aqueous gel fragrance excellent in retention performance of a liquid component containing a fragrance material having a low vapor pressure in an aqueous system or a solubilizing system.

The present invention includes (a) a nonionic surfactant represented by the following general formula (a1) [hereinafter referred to as component (a)], (b) a compound represented by the following general formula (b1), and a general formula ( a compound selected from the compounds represented by b2) [hereinafter referred to as component (b)], (c) a fragrance material having a log P of 1 to 6 containing 30 to 100% by mass and a log P of 4 to 6 Containing 10 to 80% by mass (hereinafter referred to as component (c)), (d) a water absorbent resin (hereinafter referred to as component (d)), and water, and the mass of (a) / (b) It relates to an aqueous gel fragrance with a ratio of 5/95 to 55/45.
_{HO - [(C 2 H 4} O) m / (C 3 H 6 O) n] -H (a1)
[Wherein, m is a number from 1 to 30, n is a number from 5 to 100, and “/” may be a random or block arrangement of (C ₂ H ₄ O) and (C ₃ H ₆ O). Means. ]

Wherein R ^1b represents a hydrocarbon group having 7 to 19 carbon atoms, and R ^2b and R ^3b each independently represents a group selected from an alkyl group having 1 to 3 carbon atoms or a hydroxy group having 1 to 3 carbon atoms. And p represents a number from 2 to 5.)

(In the formula, R ^2b and R ^3b each independently represent a group selected from an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ^4b represents a hydrocarbon group having 8 to 20 carbon atoms. Represents.)

  According to this invention, it is an aqueous gel fragrance | flavor using the fragrance | flavor which contains a certain amount or more of fragrance | flavor raw materials whose logP is 4-6, Comprising: The fragrance | flavor with low vapor pressure in the water system or solubilization system whose logP is 1-6 Provided is an aqueous gel fragrance that is excellent in holding performance of a liquid component containing a material and that does not cause separation of the liquid component over time.

[(A) component]
The component (a) nonionic surfactant is represented by the general formula (a1) from the viewpoint of liquid retention and fragrance sustainability, and a hydrophobic polypropylene glycol unit having excellent compatibility with a fragrance. Group, having a polyethylene glycol unit as a hydrophilic group. In the general formula (a1), the arrangement of (C ₂ H ₄ O) and (C ₃ H ₆ O) may be random or block, but the block addition type is more preferable from the viewpoint of liquid retention and fragrance persistence. More preferable than the random addition type. Specifically, at least one selected from the following general formulas (a2) to (a4) is preferable.
HO- (EO) _a- (PO) _b- (EO) _c- H (a2)
HO- (PO) _x- (EO) _y- (PO) _z- H (a3)
HO- (EO) _y- (PO) _b- H (a4)
[In the formulas (a2), (a3), and (a4), EO represents an oxyethylene group, PO represents an oxypropylene group, and x, z, and b each represent an average added mole number of propylene oxide and are greater than 0. Yes, in terms of retention performance of the liquid component containing the specific perfume material, 5 ≦ x + z ≦ 100, preferably 10-60, b ≦ 100, preferably 10-60, y and a, c are Each represents the average number of moles of ethylene oxide added, 1 ≦ y ≦ 30, preferably 1-25, a and c are each greater than 0, 1 ≦ a + c ≦ 30, preferably 1-25 is there. ]

  In terms of the retention performance of the liquid component containing the specific perfume material, more preferably, at least one selected from the nonionic surfactant of the general formula (a2) and the nonionic surfactant of the general formula (a4) And most preferably one or more nonionic surfactants selected from nonionic surfactants of the general formula (a2).

[Component (b)]
The component (b) is a compound represented by the general formula (b1) and the general formula from the viewpoint of solubilizing the mixture of the component (a) and the component (c) and enhancing the liquid retention and the scent sustainability. It is a compound selected from the compounds represented by (b2).

In general formula (b1), R ^1b represents a hydrocarbon group having 7 to 19 carbon atoms. From the point of persistence of the scent, preferably a hydrocarbon group having 11 to 15 carbon atoms, more specifically heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group Group selected from a group, a hexadecyl group, a heptadecyl group, an octadecyl group and a nonadecyl group, and preferably a group selected from an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group and a heptadecyl group. More preferably, it is a group selected from an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group and a pentadecyl group. Most preferred is an undecyl group and / or a tridecyl group. p is a number of 2 to 5, preferably 3. R ^2b and R ^3b in the general formula (b1) are preferably a methyl group or an ethyl group.

In general formula (b2), R ^4b represents a hydrocarbon group having 8 to 20 carbon atoms. From the point of persistence of the scent, preferably a hydrocarbon group having 10 to 16 carbon atoms, more specifically octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group Group, heptadecyl group, and octadecyl group. More preferred are decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group and hexadecyl group. Most preferred is a dodecyl group and / or a tetradecyl group. R ^2b and R ^3b in the general formula (b2) are preferably methyl groups.

  The component (b) is produced by uniformly dispersing or solubilizing the component (c) in the fragrance-containing liquid mixture with a small amount of surfactant during production, and (d) the water-absorbent resin is efficiently impregnated with the fragrance-containing liquid mixture. From the viewpoint of making it possible, or from the viewpoint of further enhancing the sustainability of the scent, it is a preferred component. The component (b) is preferably a compound represented by the general formula (b1).

[Component (c)]
The fragrance | flavor which is (c) component of this invention means the fragrance | flavor raw material itself whose logP is 1-6, or the composition containing 1 or more types of this. From the viewpoint of promoting impregnation of a liquid mixture containing a large amount of a fragrance that is difficult to impregnate a water-absorbent resin, and the fragrance of an aqueous gel fragrance, the content of the fragrance material having a log P of 1 to 6 in the fragrance is 30 to 100 mass. %, Preferably 40 to 100% by mass, more preferably 50 to 100% by mass. Moreover, 10-80 mass%, Preferably 14-70 mass%, More preferably, 18-60 mass% is contained in the fragrance | flavor raw material of the range whose logP is 4-6 by the point of fragrance persistence. The present invention uses a fragrance containing 30 to 100% by mass of a fragrance material having a log P of 1 to 6 and containing 10 to 80% by mass of a fragrance material having a log P of 4 to 6, and Since an aqueous gel fragrance that is rapidly absorbed into the water-absorbent resin and has excellent fragrance sustainability is obtained, it has great technical significance.

  Here, “log P” is a logarithmic value of the 1-octanol / water partition coefficient of the compound, and in the partition equilibrium when the compound is dissolved as a solute in the two-liquid solvent system of 1-octanol and water, It means the ratio of the equilibrium concentration of solute in each solvent and is generally indicated in the form of log “log P” with respect to the base 10. That is, logP is an index of lipophilicity (hydrophobicity). The larger the value, the more hydrophobic, and the smaller the value, the more hydrophilic.

  For logP, see, for example, Daylight Chemical Information Systems, Inc. It is possible to refer to logP published in a database available from (Daylight CIS) or the like as an actual measurement value. Further, when there is no actual measurement value, it can be calculated by a program “CLOGP” (Daylight CIS) or the like, and among them, calculation by the program “CLOGP” is preferable because of high reliability.

  In the program “CLOGP”, the value of “calculated logP (ClogP)” calculated by the Hansch, Leo fragment approach is output together with the measured value of logP, if any. The fragment approach is based on the chemical structure of the compound and takes into account the number of atoms and the type of chemical bond (A. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. et al. B. Taylor and CA A. Ramsden, Eds., P. 295, Pergamon Press, 1990). Since this ClogP is currently the most common and reliable estimate, it is preferable to use ClogP instead when there is no measured value of logP when selecting a compound. In the present invention, either an actual measured value of logP or ClogP calculated by the program “CLOGP” may be used. However, when there is an actual measured value, it is preferable to use the actual measured value.

  Although it does not specifically limit, the specific example of the fragrance | flavor raw material whose ClogP is less than 1-4 is shown below. The numbers in () are ClogP values.

  Raspberry ketone (1.1), heliotropin (1.1), fructon (1.1), 2-phenylethyl alcohol (1.2), vanillin (1.3), helional (1.4), cinnamic alcohol (1.4), coumarin (1.4), anisaldehyde (1.8), caron (1.8), ethyl vanillin (1.8), indole (2.1), phenylethyl acetate (2.1 ), Styrylyl acetate (2.3), methyl dihydrojasmonate (2.4), eugenol (2.4), isoeugenol (2.6), cis-jasmon (2.6), geraniol (2. 6), linalool (2.6), nerol (2.8), hexyl acetate (2.8), dihydromyrcenol (3.0), citral (3.1), citronellol (3.3), linali Acetate (3.5), Neryl acetate (3.6), Tetrahydrogeraniol (3.7), Ambrinol (3.8), Aldehyde C-14 Peach (3.8), Liliar (3.9), Tetrahydro Mugor (3.5), β-ionone (3.8), geranyl acetate (3.7), ethyl 3-methyl-3-phenylglycidate (2.7), δ-damascone (3.6) Allyl heptanoate (3.4), δ-undecalactone (3.8), phenylethylphenyl acetate (3.8).

  Although it does not specifically limit, the specific example of the fragrance | flavor raw material whose ClogP is 4-6 is shown below. The numbers in () are ClogP values.

  P-t-butylcyclohexyl acetate (4.0), amylcinnamic aldehyde dimethyl acetal (4.0), 5- (2,6,6-trimethyl-2-cyclohexen-1-yl) -3-methyl-3 -Buten-2-one (4.0), 2-phenylethyl benzoate (4.1), diphenylmethane (4.1), γ-undecalactone (4.1), tert-butylcyclohexyl acetate ( 4.1), p-methyl-isopropylbenzene (4.1), isobutylquinoline (4.2), geranyl anthranilate (4.2), auranthiol (4.2) 4- (2,2, 5,6-tetramethyl-2-cyclohexen-1-yl) -3-buten-2-one (4.2), hydroxycitronellal methylanthranilate (4.2), diphenyl oxide (4) 2), acetyl cedrene (4.2), citronellyl acetate (4.2), γ-n-methyl ionone (4.3), amylcinnamic aldehyde (4.3), damacenone (4.3), 10- Oxadecanolide (4.3), 11-oxadecanolide (4.3), γ-dodecalactone (4.4), limonene (4.4), benzyl salicylate (4.4), γ-terpinene (4.4), p-menta-1,8-diene (4.4), citronellilnitrile (4.4), 2,2,5-trimethyl-5-pentylcyclopentanone (4.5), flora mat (4.5) , Cedrol (4.5), patchouli alcohol (4.5), isoamyl salicylate (4.6), ethylene brushate (4.6), nerolidol (4.6), 7-acetyl-1,2,3 , 4, 5, 6, 7 , 8-octahydro-1,1,6,7-tetramethylnaphthalene (4.7), hexenyl salicylate (4.7), bisabolol (4.7), 1- (2,6,6-trimethyl-1- Cyclohexen-1-yl) -2-buten-1-one (4.7), β-damascone (4.7), 3,7,11-trimethyl-2,6,10-dodecatrien-12-ol ( 4.8), methyl dihydrojasmon (4.8), p-cymene (4.9), ethyl undecylenate (4.9), vetiberyl acetate (4.9), miradil acetate (4.9), cedryl formate (5.1), cedryl methyl ether (5.1), linalyl benzoate (5.2), geranyl phenyl acetate (5.2), 3α, 6,6,9α-tetramethyldodecahydronaphtho [2, 1-b] furan (5. ), Hexyl salicylate (5.3), cyclohexyl salicylate (5.3), ambroxan (5.3), cedolyl acetate (5.4), muskindanone (5.5), hexylcinnamic aldehyde (5. 5), cinnamyl cinnamate (5.5), galaxolide (5.5), 6-acetyl-1,1,2,3,3,5-hexamethylindane (5.7), 1- (2,2 , 6-trimethylcyclohexyl) -3-hexanol (5.9), fantolide (6.0).

[Component (d)]
The water-absorbing resin (d) has a water absorption amount of 10 to 300 g, preferably 10 to 250 g, more preferably 20 to 20 g of ion-exchanged water per 1 g of the water-absorbing resin under an environmental condition of 20 ° C. What is 200 g is suitable. If this water absorption is 10 g or more, the water-absorbing resin absorbs and swells the fragrance-containing liquid mixture at the time of production, and the design property of the aqueous gel fragrance obtained is better. The strength of the fragrance becomes more sufficient.

  As the component (d), a water-absorbing resin containing a polymer containing a carboxylic acid group and / or a carboxylic acid group as a structural unit is preferable. For example, a hydrolyzate of starch-acrylonitrile graft copolymer, starch-acrylic acid ester (Partial) neutralized product of copolymer, saponified product and partially saponified product of vinyl acetate-acrylic ester copolymer, hydrolyzate of acrylonitrile copolymer or acrylamide copolymer, modified polyvinyl alcohol, partially neutralized product Polyacrylate, isobutylene-maleic anhydride copolymer, crosslinked polyacrylate, crosslinked acrylic acid (salt) -acrylamide copolymer, crosslinked isobutylene-maleic anhydride copolymer, etc. In that case, it can be used alone or as a mixture of two or more. Acrylic acid (salt) means acrylic acid and / or acrylate.

  Preferred water-absorbing resins are polyacrylate cross-linked products, acrylic acid (salt) -acrylamide copolymer cross-linked products, and isobutylene-maleic anhydride copolymer cross-linked products, particularly in terms of water separation and scent persistence. In view of the above, a crosslinked product of acrylic acid (salt) -acrylamide copolymer is preferred.

  As the crosslinked polyacrylate, for example, those described in JP-A-8-337726 and JP-A-8-127725 can be used. Moreover, the water absorbing resin described in Unexamined-Japanese-Patent No. 2000-212354 and Unexamined-Japanese-Patent No. 2006-167202 can be used for a crosslinked isobutylene-maleic anhydride copolymer, for example. Furthermore, as the acrylic acid (salt) -acrylamide copolymer cross-linked product, water-absorbing resins described in JP 2007-291145 A, JP 2007-291146 A, and JP 2007-270100 A can be used. .

  The form of component (d) is preferably spherical. When the water-absorbing resin is packed in a container, if it is spherical, the area where the resins are in close contact with each other and the gap is increased, so that the contact area with the air is increased, which is favorable in terms of smell. Moreover, 500-4000 micrometers is suitable for the average particle diameter in the dry state before making a fragrance | flavor containing liquid mixture contact at the time of manufacture. The average particle size is determined according to a JIS test sieve standard sieve [for example, no. 5-No. 35 (4 mm to 500 μm with a nominal aperture)].

  (D) Although it does not restrict | limit especially as a commercial item of a component, For example, as an acrylic acid (salt) bridge | crosslinking body, Aquacat CA manufactured by Nippon Shokubai, Aqua Keep manufactured by Sumitomo Seika, Sun manufactured by Sanyo Kasei Fresh, aqua pearl, acrylamide-acrylic acid (salt) copolymer cross-linked product is HISOBEAD made by AK Chemtech Co., Ltd., and isobutylene-maleic anhydride copolymer cross-linked product is Kuraray Chemical made aqua beads, polyoxyalkylene Examples of the crosslinked oxide include Aqua Coke manufactured by Sumitomo Seika.

[Other ingredients]
In the present invention, a fragrance material other than a fragrance material having a log P of 1 to 6 can be used, although it is optional. For example, ethyl acetate (0.71), ethyl acetoacetate (0.33), ethyl maltol (0.47), maltol (−0.062), galaxolide (6.1), tibertolide (6.2), ilangen (6.3), pentalide (6.3), ambletlide (6.3), β-caryophyllene (6.3), hexadecanolide (6.8), kadinene (7.3) and the like. The numbers in () are ClogP values.

  In addition, the aqueous gel fragrance of the present invention includes, as other components, solvents generally added to stationary aqueous gel fragrances, oils, salts such as sodium sulfate and N, N, N-trimethylglycine, pH It can contain a regulator, an antioxidant, a chelating agent, an antiseptic, a bactericide / antibacterial agent, a dye, an ultraviolet absorber, and the like.

[Aqueous gel air freshener]
The aqueous gel fragrance of the present invention has a mass ratio of (a) / (b) of 5/95 to 55/45, preferably 10/90 to 50/50, from the viewpoint of the retention performance of the liquid component. Preferably it is 20 / 80-49 / 51.

  Moreover, from the viewpoint of fragrance sustainability, the mass ratio of the component (a) to the component (c) is preferably (a) component / (c) component = 80/20 to 16/84, more preferably 75/25. 20/80, more preferably 67/33 to 25/75, and most preferably 50/50 to 33/67.

  Moreover, the aqueous gel fragrance | flavor of this invention has (a) component 0.1-20 mass%, Furthermore 0.2-10 mass%, (b) 0.2-30 mass%, Furthermore 0.2 -25% by mass, further 0.5-15% by mass, component (c) 1-10% by mass, further 1-8% by mass, component (d) 2-12% by mass, further 3-8% by mass It is preferable from the viewpoint of the scent sustainability. The water content is preferably 30 to 96% by mass, more preferably 50 to 95% by mass, and even more preferably 70 to 94% by mass.

  The aqueous gel fragrance of the present invention comprises (a) 0.1 to 20% by mass, (b) 0.2 to 25% by mass, (c) 1 to 10% by mass and a fragrance containing water. A liquid mixture (hereinafter referred to as a fragrance-containing liquid mixture (A)) and a water-absorbent resin of component (d) are brought into contact with each other, and the water-absorbent resin of component (d) is impregnated with the liquid mixture of fragrance Is preferable from the viewpoint of sustainability of the scent.

  The fragrance-containing liquid mixture (A) is preferably a composition containing the component (a), the component (b), the component (c) and water, and further the form of an aqueous solution from the viewpoint of ease of production of the aqueous gel fragrance. It is preferable to use ion-exchanged water from which metals present in the water are removed.

  0.1-20 mass% is preferable, as for content of (a) component in a fragrance | flavor containing liquid mixture (A), 0.2-15 mass% is more preferable, 0.5-10 mass% is still more preferable, 0.8-5 mass% is especially preferable. Moreover, 0.2-25 mass% is preferable, as for content of (b) component in a fragrance | flavor containing liquid mixture (A), 0.5-15 mass% is more preferable, and 0.8-10 mass% is further. 1 to 8% by mass is preferable. Moreover, 1-10 mass% is preferable, as for content of (c) component in a fragrance | flavor containing liquid mixture (A), 1-8 mass% is more preferable, 1-6 mass% is still more preferable, 1-4 mass % Is particularly preferred.

  The pH of the fragrance-containing liquid mixture (A) at 20 ° C. is preferably 3-8, particularly preferably 4-7, and high fragrance persistence can be obtained at such pH.

  In the present invention, the fragrance-containing liquid mixture (A) is contacted with the water-absorbent resin of the component (d), and the fragrance-containing liquid mixture (A) is impregnated in the component (d). The water content of the component (d) at the time of contact is preferably 20% by mass or less, and more preferably 10% by mass or less in terms of obtaining an aqueous gel fragrance having a high scent persistence. When the fragrance-containing liquid mixture (A) and the component (d) are brought into contact with each other, the temperature of the fragrance-containing liquid mixture (A) or the component (d) is preferably in the range of 0 to 40 ° C. When the fragrance-containing liquid mixture (A) and the component (d) are brought into contact with each other, they may be allowed to stand or may be weakly stirred so that the water absorbent resin is not damaged. The production method of the present invention is suitable in that the fragrance-containing liquid mixture (A) can usually permeate and hold inside the water-absorbent resin even if it is allowed to stand still from the standpoint of production simplicity. With this production method, an aqueous gel fragrance in which the component (c) in the fragrance-containing liquid mixture (A) is supported on the component (d) is obtained. The mixing ratio of the fragrance-containing liquid mixture (A) and the component (d) depends on the water absorption capacity of the component (d), but the fragrance-containing liquid mixture (A) / (d) component = 100/1, depending on the mass ratio. It can be produced under the conditions of 5/1, further 50/1 to 10/1.

  The aqueous gel fragrance produced by the above method contains (a) component, (b) component, (c) component, (d) component, and water.

  The aqueous gel fragrance of the present invention can be used as a fragrance as it is, but it can be a stationary fragrance comprising the aqueous gel fragrance. For example, it can be stored in a self-supporting container or the like to form a stationary fragrance.

  The container in which the aqueous gel fragrance is accommodated can contain the aqueous gel fragrance, has an open portion, and volatilizes the fragrance component [component (c)] in the aqueous gel fragrance from the open portion. As long as it can be obtained, there is no particular limitation on the shape and structure thereof, and it is also possible to use those in other parts such as the side part in addition to those having the open part in the upper part.

  As the container, plastic, glass, metal, or the like can be used, but a transparent or translucent material that can visually observe the shrinkage of the gel-like molded product, or a material that can visually recognize the inside through a slit or an opening can be used. Further, plastic containers conventionally used for fragrances and deodorants, specifically, containers of polyethylene terephthalate (PET), polypropylene, polyethylene, polystyrene, etc. are used.

  When the aqueous gel fragrance of the present invention is housed and installed in a container, the installation amount is not particularly limited, and can be appropriately selected according to characteristics such as a place to be used, a period of use, and a container shape. You may accommodate and install the water-based gel fragrance | flavor which has a mutually different color tone and / or fragrance | flavor to a container.

<Appearance of perfume-containing liquid mixture>
80 g of the fragrance-containing liquid mixture (A) prepared in Table 2 prepared using the fragrance composition shown in Table 1 and placed in a wide-mouth standard bottle (PS-No. 11) and allowed to stand at 25 ° C. for 6 hours. The appearance was evaluated. "Transparent" is almost completely solubilized and turbidity cannot be recognized by the naked eye, "Slightly turbid" is insufficiently solubilized, but 15 letters and 15 columns on the newspaper can be read through the solution in the bottle, “White turbidity” indicates a state where the solubilization is insufficient and 15-letter and 15-column text on the newspaper cannot be read through the solution in the bottle, and “separation” indicates a state where the oil component is separated due to insufficient solubilization.

<Preparation of gel fragrance>
Put 2.85 g of the fragrance-containing liquid mixture (A) of Table 2 prepared using the fragrance composition of Table 1 and 0.15 g of the water-absorbent resin in a wide-mouth standard bottle (PS-No. 6), and close the lid. The fragrance-containing liquid mixture (A) was impregnated in a water-absorbent resin, and the one left for 24 hours was used as a gel fragrance, which was used for evaluation of liquid retention and fragrance (initial and sustainability).

<Evaluation of liquid retention at the end of use>
The liquid retention at the end of use of the gel-like fragrance was determined based on the following criteria by determining whether there was a liquid that could not be retained between the gel and the gel and between the gel and the inner wall of the glass standard bottle. The determination was performed after opening the bottle mouth of the standard bottle of the gel-like fragrance prepared above and storing it in a constant temperature bath at 40 ° C. to 50 RH for 7 days, and then closing the lid again. This condition corresponds to the condition after about 20 to 40 days of use at room temperature, and reproduces the state at the end of use. The judgment value is an average value of three people.
* Liquid retention judgment criteria 3: Liquid separation is not observed inside the container including the gel bottle bottom contact part, the gel bottle side wall contact part, and between the gel and the gel.
2: Liquid is separated at at least one of the gel bottle bottom contact part, gel bottle side wall contact part, and gel-gel, but the liquid drips even if the bottle is tilted 90 degrees and left to stand for 1 hour. Absent.
1: Liquid is separated in at least one of the gel bottle bottom contact part, the gel bottle side wall contact part, and the gel-gel, and the liquid drips when the bottle is tilted by 90 degrees and allowed to stand for 1 hour.

<Evaluation of fragrance standing (initial scent intensity) and scent persistence>
The lid of the wide-mouth standard bottle containing the gel-like fragrance immediately after preparation is opened, and the fragrance of the bottle mouth is evaluated after 24 hours at 25 ° C. This is regarded as the initial fragrance. Next, with the lid open, the scent at the bottle mouth was evaluated 16 days after standing at 25 ° C., and the scent persistence was evaluated.

Evaluation of the initial fragrance is based on the fragrance intensity of an aqueous solution obtained by diluting the fragrance-containing liquid mixture used in the gel fragrance corresponding to each of the Examples and Comparative Examples in stages with water. In contrast, the fragrance level was relatively compared according to the following evaluation standards for fragrance intensity. All were evaluated by the average value of the results of 5 judges who engaged in the work of incense for more than 5 years.
* Evaluation criteria for fragrance strength 5: Strength equal to or better than 50% aqueous solution 4: Strength equivalent to 25% aqueous solution 3: Strength equivalent to 5% aqueous solution 2: Strength equivalent to 1% aqueous solution 1: 0 .Same strength as 25% aqueous solution 0: Weaker than 0.25% aqueous solution

Moreover, the evaluation criteria of fragrance persistence are as follows, and all were evaluated by the average value of the results of five judges who engaged in the work of fragrance for 5 years or more.
* Evaluation criteria for fragrance persistence 5: Same strength as initial (25 ° C, after 24 hours) 4: Slightly weaker than initial (25 ° C, after 24 hours) 3: Initial (25 ° C, 24 hours after) After) Weaker 2: Much weaker than initial (25 ° C, after 24 hours) 1: Almost no fragrance

  Table 1 shows the fragrance composition. The results are shown in Table 2.

(Note) The components in Table 2 are as follows.
A-1: Adeka Pluronic L-61, a nonionic surfactant (block adduct of EO / PO / EO) of a + c = 5 and b = 30 in the general formula (a2)
A-2: Adeka Pluronic L-71, a nonionic surfactant having a + c = 5 and b = 35 in the general formula (a2) (block adduct of EO / PO / EO)
A′-1: polyoxyethylene dodecyl ether (average number of moles of ethylene oxide added 8) [nonionic surfactant not a component (a)]
B-1: Lauroylamidopropyldimethylamine oxide c-1 Fragrance composition c-1 in Table 1
C-2: perfume composition c-2 of Table 1
D-1: “Hisobead” manufactured by AK Chemtech Co., Ltd., cross-linked water-absorbing resin of acrylamide-acrylic acid (salt) copolymer (water content 5 mass%)

Claims (3)

(A) a nonionic surfactant represented by the following general formula (a1), (b) a compound selected from a compound represented by the following general formula (b1) and a compound represented by the general formula (b2), ( c) The fragrance | flavor which contains 30-100 mass% of fragrance | flavor raw materials whose log P is 1-6, and 10-80 mass% of fragrance | flavor raw materials whose log P is 4-6, (d) Water-absorbing resin and water are contained. The aqueous gel fragrance | flavor whose mass ratio of (a) / (b) is 5 / 95-55 / 45.
_{HO - [(C 2 H 4} O) m / (C 3 H 6 O) n] -H (a1)
[Wherein, m is a number from 1 to 30, n is a number from 5 to 100, and “/” may be a random or block arrangement of (C ₂ H ₄ O) and (C ₃ H ₆ O). Means. ]

Wherein R ^1b represents a hydrocarbon group having 7 to 19 carbon atoms, and R ^2b and R ^3b each independently represents a group selected from an alkyl group having 1 to 3 carbon atoms or a hydroxy group having 1 to 3 carbon atoms. And p represents a number from 2 to 5.)

(In the formula, R ^2b and R ^3b each independently represent a group selected from an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ^4b represents a hydrocarbon group having 8 to 20 carbon atoms. Represents.)   The aqueous gel fragrance according to claim 1, wherein (d) the water-absorbent resin contains a polymer containing a carboxylic acid group and / or a carboxylic acid group as a constituent unit.   A fragrance-containing liquid mixture containing 0.1 to 20% by mass of (a), 0.2 to 30% by mass of (b), 1 to 10% by mass of (c) and water, and (d) a water absorbent resin. The aqueous gel fragrance according to claim 1 or 2, wherein the fragrance-containing liquid mixture is impregnated with the (d) water-absorbent resin.