JP5356751B2 - Aqueous gel air freshener - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water based gel for aromatic agent which is excellent in sustainment of an aroma, and a stationary aromatic agent. <P>SOLUTION: The water based gel for aromatic agent includes (a) a silicone compound, (b) a perfume, (c) a surfactant, and (d) a water-absorptive resin, wherein (a) is one or more silicone compounds selected from among dimethyl silicone, a polyether-modified silicone and an amino-modefied silicone; (b) is a perfumery compound having a lipophilicity index logP of 1-4; and (c) is a nonionic surfactant represented by the formula: RO-(AO)n-H [wherein R is an 8-24C alkyl group or alkenyl group, AO is an oxyethylene group and/or an oxypropylene group, and n=2-100]; and (d) is an acrylic acid base water-absorptive resin, or a water-absorptive resin made by crosslinking a copolymer of isobutylene and maleic acid anhydride. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an aqueous gel fragrance and a stationary fragrance.

  Air fresheners that use aqueous gels (hereinafter sometimes referred to as aqueous gel air fresheners) have recently been widely used in stationary air fresheners due to their superior aesthetic appearance and the ability to spill liquid from containers. .

  As the aqueous gel fragrance, for example, a type prepared by mixing a fragrance blending solution and a gelling agent or a type prepared by absorbing a fragrance blending solution into an absorbent resin is known (Patent Documents 1 to 4). ).

Compared with liquid fragrances, aqueous gel fragrances have the characteristic that liquid does not spill out of the container. However, from the viewpoint of absorbing the gelling agent, there is an upper limit in the amount of oil (fragrance), and the fragrance is gradually reduced. Technology such as release was insufficient. As a technique for sustained release of a liquid fragrance based on the problems of an aqueous gel fragrance, for example, mixing silicone oil and a fragrance is cited (Patent Document 5).
JP-A-9-290015 JP 2006-167202 A JP 2000-212354 A JP 2002-331023 A Japanese Patent Laid-Open No. 11-114042

  The type that mixes and adjusts the fragrance compounding solution and the gelling agent requires time and effort to uniformly disperse the gelling agent and to gelate from that state. In addition, it takes time and effort even after trying to process.

  On the other hand, the type in which the fragrance dispersion (solubilized solution) is absorbed by the water-absorbing resin can be easily prepared by simply adding the water-absorbing resin to the fragrance compounding liquid. Therefore, from the viewpoint of manufacturing, this type is considered to be excellent as a water gel type fragrance, but this type of water gel fragrance maintains the scent strength generally required for fragrances for a long time. As for the technology to do, examination is inadequate, and further improvement is desired about the sustainability of fragrance.

  Further, the technique of Patent Document 5 is said to be excellent in transparency, stability over time, and sustainability. Although it is essentially composed of silicone oil and fragrance, it is thought that the fragrance has a sustained release effect by dissolving a highly hydrophobic fragrance with high solubility in hydrophobic silicone oil, rather it is volatile. It is less effective for hydrophilic fragrances that have a high solubility in silicone oil and require a sustained release effect. In addition, from the viewpoint of container storage, when considering product forms such as carriers and absorbers that are less likely to leak, silicone oil is difficult to absorb into common water gels and is limited to pulp and some absorbent polymers. It will be

  An object of the present invention is to provide an aqueous gel fragrance and a stationary fragrance excellent in scent sustainability.

  The present invention relates to an aqueous gel fragrance containing (a) a silicone compound, (b) a fragrance, (c) a surfactant, and (d) a water absorbent resin.

  The present invention also includes (a) a silicone compound (hereinafter referred to as component (a)), (b) a fragrance (hereinafter referred to as component (b)), and (c) a surfactant (hereinafter referred to as component (c)). And a liquid mixture containing water and (d) a water-absorbent resin (hereinafter referred to as “component (d)”).

  The present invention also relates to a stationary fragrance comprising the aqueous gel fragrance of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the water-based gel fragrance | flavor excellent in the persistence of fragrance is provided. Such an aqueous gel fragrance of the present invention can provide a stationary fragrance excellent in fragrance persistence.

[(A) component]
The component (a) is preferably one or more silicone compounds selected from dimethyl silicone (also referred to as dimethicone), polyether-modified silicone, and amino-modified silicone, more preferably polyether-modified silicone.

The dimethyl silicone preferably has a viscosity at 25 ° C. of 100 to 100,000 mm ² / s, and more preferably 200 to 100,000 mm ² / s. Moreover, it is preferable to use what was made into the dimethyl silicone emulsion by adding an emulsifier.

  Specific examples of dimethyl silicone include SH-200, CF2238, DC-1716, XS65-C0077, XS65-C0104, BY22-029, and BY22-060 manufactured by Toray Dow Corning Silicone. .

The polyether modified silicone used in the present invention, a viscosity at 25 ° C., is preferably a 30~30000mm ² / s, still more preferably ^{40~25000mm 2 / s, 500~20000mm 2 /} s is particularly preferred.

  As the polyether group, a polyoxyethylene group, a polyoxypropylene group, a polyoxyalkylene group in which an oxyethylene group and an oxypropylene group are added in a block shape or at random are suitable, and a compound in which a polyether group is grafted to a silicone main chain A compound in which silicone and a polyether group are bonded in a block shape can be used.

  More specifically, a compound represented by the following general formula (a1) and a compound represented by the general formula (a2) can be exemplified.

[Wherein, R ^1a and R ^2c are each an alkyl group or hydroxy group having 1 to 3 carbon atoms, R ^1c and R ^2a are each a hydrogen atom or an alkyl group or hydroxy group having 1 to 3 carbon atoms, and EO Is an ethyleneoxy group, PO is a propyleneoxy group, and R ^1b and R ^2b are each an alkylene group having 2 to 5 carbon atoms. c, d, e, f, g, h, i, j, k, and l are selected so as to fall within the preferred viscosity and preferred cloud point range of the present invention. Note that d, e, and g + i are numbers of 1 or more. ]

  Specific preferred compounds of the polyether-modified silicone include KF-351, KF-352, KF-353, KF-6009, KF-6011, KF-6012, KF-6015, KF-6017 manufactured by Shin-Etsu Chemical Co., Ltd. , KF-6025, SH-3775M, SH-3748, SH-349, L-7001, FZ-2203, FZ-2222, manufactured by Toray Dow Corning Silicone Co., Ltd., Momentive Performance Materials Japan GK And TSF-4445, TSF-4446, and TSF-4460.

Examples of the amino-modified silicone include a compound represented by the general formula (a3). The amino-modified silicone of the general formula (a3) has a kinematic viscosity at 25 ° C. of 50 to 30000 mm ² / s, more preferably 300 to 20000 mm ² / s, and amino equivalent (molecular weight per nitrogen atom, amino equivalent = molecular weight). The molecular weight is a value determined by gel permeation chromatography with polystyrene as the standard, and the number of nitrogen atoms can be determined by elemental analysis) is 100 to 10,000, and more preferably 1000 to 8,000. It is preferable.

[Wherein R ^3a represents a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms or a hydrogen atom, and R ^3b represents an alkyl group having 1 to 3 carbon atoms, hydroxy Represents a group selected from a group or a hydrogen atom, A represents a side chain having at least one amino group, and R ^3c represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. p and q each represent an average degree of polymerization, and are selected so that the kinematic viscosity at 25 ° C. and the amino equivalent of the compound are in the above ranges. R ^3a , R ^3b and R ^3c may be the same or different, and a plurality of R ^3b may be the same or different. ]

In the compound of the general formula (a3), R ^3a is preferably a methyl group or a hydroxy group, R ^3b is preferably a methyl group or a hydroxy group, and R ^3c is preferably a methyl group or a hydrogen atom. p is preferably a number of 10 to 10,000, more preferably a number of 20 to 3,000. q is preferably a number of 1 to 1,000, more preferably a number of 1 to 100. The weight average molecular weight of the compound of the general formula (a3) is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000, and particularly preferably 8,000 to 50,000.

In the general formula (a3), examples of the side chain A having an amino group include the following.
-C ₃ H ₆ -NH _{2
-C 3 H 6 -NH-C 2} H 4 -NH 2
_{-C 3 H 6 -NH- [C 2} H 4 -NH] e -C 2 H 4 -NH 2
_{-C 3 H 6 -NH (CH 3} )
_{-C 3 H 6 -NH-C 2} H 4 -NH (CH 3)
_{-C 3 H 6 -NH- [C 2} H 4 -NH] f -C 2 H 4 -NH (CH 3)
_{-C 3 H 6 -N (CH 3} ) 2
_{-C 3 H 6 -N (CH 3} ) -C 2 H 4 -N (CH 3) 2
_{-C 3 H 6 -N (CH 3} ) - [C 2 H 4 -N (CH 3)] g -C 2 H 4 -N (CH 3) 2
_{-C 3 H 6 -NH-cyclo-} C 5 H 11
Here, e, f, and g are numbers 1 to 30, respectively.

The amino-modified silicone is, for example, a basic product such as sodium hydroxide obtained by hydrolyzing an organoalkoxysilane represented by the general formula (a4) with an excess of water and dimethylcyclopolysiloxane. It can be produced by heating to 80 to 110 ° C. using a catalyst for an equilibrium reaction, and neutralizing the basic catalyst with an acid when the reaction mixture reaches the desired viscosity. (See Japanese Patent Laid-Open No. 53-98499)
H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ (a4)

Examples of the amino-modified silicone that can be used in the present invention include SF8451C (viscosity 600 mm ² / s (25 ° C.), amino equivalent 1700), SF8452C (viscosity 700 mm ² / s (25) manufactured by Toray Dow Corning Silicone Co., Ltd. ° C), amino equivalent 6400), SF8457C (viscosity 1200 mm ² / s (25 ° C), amino equivalent 1800), SF8417 (viscosity 1200 mm ² / s (25 ° C), amino equivalent 1800), BY16-849 (viscosity 1300 mm ² / s (25 ° C.), amino equivalent 600), BY16-850 (viscosity 1100 mm ² / s (25 ° C.), amino equivalent 1100), BY16-892 (viscosity 1100 mm ² / s (25 ° C.), amino equivalent 2000), BY16 -897 (viscosity ^{900mm 2 / s (25 ℃)} , amino equivalent of 290 ), BY16-898 (viscosity ^{1300mm 2 / s (25 ℃)} , amino eq 2900), manufactured by Shin-Etsu Chemical (Co.) KF857, KF858, KF859, KF862 , KF8001, KF880, KF-864 ( viscosity 1700 mm ² / s (25 ° C.), amino equivalent 3800) and the like.

[Component (b)]
The component (b) of the present invention is a fragrance. Usually, a fragrance contains a plurality of fragrance compounds, but a fragrance compound alone may be used as a fragrance. The fragrance that can be used is not particularly limited, but from the viewpoint of solubilization in water, aesthetics, and fragrance, the fragrance compound with logP = 1 to 4 is 50% by mass or more, and further 55% by mass or more. The fragrance | flavor contained 60 mass% or more is suitable. That is, it is a fragrance containing 50 to 100% by mass, further 55 to 100% by mass, and further 60 to 100% by mass of a fragrance compound of log P = 1 to 4 in the fragrance.

  Here, the “log P value” 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. , Means the ratio of the equilibrium concentration of the solute in each solvent and is generally indicated in the form of log “log P” with respect to the base 10. That is, the log P value is an index of lipophilicity (hydrophobicity). The larger the value, the more hydrophobic, and the smaller the value, the more hydrophilic.

  For the log P value, see, for example, Daylight Chemical Information Systems, Inc. A logP value published in a database available from (Daylight CIS) or the like can be referred to 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 value is currently the most common and reliable estimate, it is preferable to use the ClogP value 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 a ClogP value 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.

  Specific examples of perfume compounds having ClogP of 1 to 4 include cis-3-hexenol, linalool oxide, benzyl acetate, cis-3-hexenyl acetate, linalool, nerol, geraniol, hexyl acetate, linalyl acetate, geranyl acetate, coumarin, Heliotropin, phenylethyl alcohol, vanillin, cinnamic alcohol, anis alcohol, cinnamic aldehyde, l-carvone, methyl anthranilate, methyl benzoate, benzophenone, eugenol, benzyl propionate, allyl 2-benoxylglycolate, borneol, 4-terpineol 1,8-cineole, methylisoeugenol, citral, estragole, l-menthol, citronellol, citronellal, anethole, carvacrol, timo , Cyclamen aldehyde, tetrahydro linalool, beta-irone, .gamma.-undecalactone, and the like methyl benzoate.

[Component (c)]
Examples of the component (c) include one or more surfactants selected from nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.

  Specific examples of the nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyalkylene aryl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene castor Oil, polyoxyethylene hydrogenated castor oil, and the like. When a nonionic surfactant is used alone, it is desirable that the HLB calculated from the Griffin equation is 8 to 15 from the viewpoint of dispersibility of the fragrance. The nonionic surfactant is preferably a polyoxyalkylene alkyl ether, more preferably a polyoxyethylene alkyl ether, an alkylene oxide, more preferably an average added mole number of ethylene oxide of 1 to 50, more preferably 5 to 20, an alkyl group. The number of carbon atoms is preferably 8-18, more preferably 10-18.

Preferred nonionic surfactants as (c) include nonionic surfactants represented by the following general formula (c1).
R—O— (AO) _n —H (1)
[In the formula, R is an alkyl group having 8 to 24 carbon atoms or an alkenyl group having 8 to 24 carbon atoms, AO is at least one selected from ethylene oxide and propylene oxide, and the addition form is random addition or block addition. But you can. Moreover, n shows an average added mole number, and n = 2-100, Preferably it is 2-50, More preferably, it is 5-20. ]

  The anionic surfactant includes an ether carboxylic acid having a hydrocarbon group having 8 to 24 carbon atoms or a salt thereof, a sulfate ester or an ether sulfate having a hydrocarbon group having 8 to 24 carbon atoms, or a salt thereof. A sulfonate having a hydrocarbon group having 8 to 24 carbon atoms, a sulfosuccinate having one or two hydrocarbon groups having 8 to 24 carbon atoms, a phosphate ester having a hydrocarbon group having 8 to 24 carbon atoms, or Examples thereof include ether phosphate esters or salts thereof, fatty acid salts having a hydrocarbon group having 8 to 24 carbon atoms, and acylated amino acid salts having a hydrocarbon group having 8 to 24 carbon atoms.

  Examples of the cationic surfactant include alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, triethanolamine difatty acid ester quaternary salt, fatty acid monoester monoamide salt of N-hydroxyethyl-N-methyl-propanediamine, Examples thereof include alkylbenzyldimethylammonium salt, alkylammonium salt, alkylpyridinium salt and the like. As the cationic surfactant, an alkyl (carbon number 8 to 18) trimethylammonium salt, a dialkyl (carbon number 8 to 18) dimethylammonium salt, or an alkyl (carbon number 8 to 18) benzyldimethylammonium salt is preferable.

  In addition, as the amphoteric surfactant, betaine-type amphoteric surfactant [coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, Lauryl hydroxysulfobetaine, lauroylamidoethylhydroxyethylcarboxymethylbetaine hydroxypropyl sodium phosphate, etc.] and amino acid type amphoteric surfactants [sodium β-laurylaminopropionate, etc.].

  (C) As a component, a nonionic surfactant is preferable from a viewpoint of the liquid absorbency of a gel and the solubilization ability of a fragrance | flavor. Moreover, it is preferable that a nonionic surfactant is included as (c) component, and the ratio of a nonionic surfactant in (c) component is 20-100 mass%, Furthermore, it is 50-100 mass%. preferable.

[Component (d)]
As the component (d) of the present invention, a water absorbent resin having a carboxylic acid group and / or a neutralizing group thereof as a structural unit is preferable. (D) A component may be used independently or may be used in combination of 2 or more types. The component (d) is preferably an absorptive carrier made of a polymer compound having a carboxylic acid group and / or a neutralizing group as a constituent unit in the molecule, and contains the components (a) to (c) and water. Those that can also function as a gelling agent for the mixture are preferred.

  As component (d), (1) crosslinked or self-crosslinked polyacrylate by reverse phase suspension polymerization method, (2) crosslinked by aqueous solution polymerization (adiabatic polymerization, thin film polymerization, spray polymerization, etc.) Polyacrylic acid and / or a salt thereof, (3) a starch-acrylic acid copolymer and / or a cross-linked product thereof, (4) a saponified copolymer of a vinyl ester and an unsaturated carboxylic acid or a derivative thereof, (5 ) A cross-linked acrylic acid copolymer and / or a salt thereof, copolymerized with a monomer containing a sulfonic acid group or a neutralizing group thereof, (6) a cross-linked isobutylene-maleic anhydride copolymer, (7 ) Hydrolyzate of starch-acrylonitrile copolymer, (8) crosslinked carboxymethylcellulose derivative, (9) copolymer of crosslinked acrylic acid and / or salt thereof and acrylamide, etc. And the like. In the above, the salt is usually a sodium salt and / or a potassium salt, but may be a salt such as a quaternary ammonium salt, an ammonium salt or an amine salt depending on the application. From the viewpoint of water absorption, a water absorption resin selected from a water absorbent resin having acrylic acid and / or its neutralizing group as a structural unit, and a water absorbent resin crosslinked with a copolymer having isobutylene and maleic anhydride as a structural unit. Resins are preferred.

  Specific commercially available water-absorbing resins selected from water-absorbing resins having acrylic acid and / or a neutralizing group thereof as a structural unit, and water-absorbing resins crosslinked with a copolymer having isobutylene and maleic anhydride as structural units. The following can be mentioned as goods. Examples of acrylic polymers include HISOB (manufactured by Ai Seimitsu Chemical Co., Ltd., water absorption ratio of deionized water (hereinafter referred to as water absorption resin) of 100 to 200 times), Aquaric CA K4 (manufactured by Nippon Shokubai Co., Ltd.). , Water absorption ratio 250 to 350 times), Aquaric CA H2 (manufactured by Nippon Shokubai Co., Ltd., water absorption ratio 150 to 250 times), Aquaric CA H3 (manufactured by Nippon Shokubai Co., Ltd., water absorption ratio 70 to 140 times), Sunfresh ST-250 (manufactured by Sundia Polymer Co., Ltd., absorption ratio 700 times), Sunfresh ST-250MPS (manufactured by Sundia Polymer Co., Ltd., absorption ratio 700 times), Sunfresh ST-500D (manufactured by Sundia Polymer Co., Ltd., Absorption capacity is 400 times), Sun Fresh ST-500MPSA (Sundia Polymer Co., Ltd.) Manufactured, absorption magnification is 400 times), Sun Fresh ST-573 (manufactured by Sundia Polymer Co., Ltd., absorption magnification is 400 times), Aqua Pearl DSC30 (manufactured by Sundia Polymer Co., Ltd., absorption magnification is 400 times), Aqua Pearl E-200 (Manufactured by Sundia Polymer Co., Ltd., absorption ratio is 380 times), Aqua Keep (manufactured by Sumitomo Seika Co., Ltd.) and the like. Moreover, as a crosslinked body of an isobutylene-maleic anhydride copolymer, KI gel-201K (made by Kuraray Trading Co., Ltd., water absorption ratio: 200 times), KI gel 201K-F2 (made by Kuraray Trading Co., Ltd., water absorption ratio: 170) Times), KI gel 201K-G1 (manufactured by Kuraray Trading Co., Ltd., water absorption magnification is 150 times), and the like.

  More specifically, the acrylic polymer is a crosslinked product of acrylamide-acrylic acid (salt) copolymer, and the molar ratio of acrylamide units is 50 to 95 with respect to the total of acrylamide units and acrylic acid (salt) units. What is mol% is preferable.

[Other ingredients]
In the aqueous gel fragrance of the present invention, as other components, solvents generally added to stationary aqueous gel fragrances, oil agents, salts such as sodium sulfate and N, N, N-trimethylglycine, pH adjustment Agents, antioxidants, preservatives, bactericides / antibacterial agents, pigments, UV absorbers and the like can be added.

[Aqueous gel air freshener and stationary air freshener]
The aqueous gel fragrance of the present invention contains the above components (a) to (d), but the aqueous gel fragrance of the present invention comprises (a) a silicone compound, (b) a fragrance, and (c) an interface. It can manufacture by mixing the liquid mixture containing an activator and water, and (d) water absorbing resin. That is, the aqueous gel fragrance of the present invention comprises a liquid mixture containing the above components (a) to (c) and water (hereinafter sometimes referred to as a liquid mixture according to the present invention), and a component (d). It is obtained by mixing and making the component (d) absorb the liquid mixture. In this method, the composition of the liquid mixture is directly reflected in the aqueous gel fragrance.

  The mixing ratio of the liquid mixture according to the present invention and the component (d) depends on the water absorption capacity of the component (d), but the liquid mixture / (d) component = 100 / 0.5 to 100/20, more preferably 100/2. ~ 100/10 (mass ratio) is preferred.

  In the aqueous gel fragrance of the present invention, the mass ratio of the component (a) to the component (b) is (a) / (b), 1000/1 to 1/100, further 100/1 to 1/50, In particular, the ratio is preferably 10/1 to 1/30 from the viewpoints of gel absorbency, gel appearance, and aroma performance.

  Moreover, in the aqueous gel fragrance | flavor of this invention, mass ratio of (a) component and (d) component is (a) / (d), and is 10/1-1/100, Furthermore, 8/1-1 / 50, particularly 5/1 to 3/100, is preferable from the viewpoint of gel absorbability.

  In addition, in the liquid mixture which concerns on this invention, content of (a) component is 0.01-30 mass%, Furthermore, 0.1-10 mass% is preferable, and content of (b) component is 0.001-30. The content of the component (c) is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, and the water content is 50 to 99.% by mass. 5 mass%, Furthermore, 70-90 mass% is preferable. Water is the balance of the liquid mixture. Below the lower limit, the initial scenting is extremely reduced. Moreover, when it exceeds an upper limit, it is not preferable from the deterioration of storage stability and the fall of gel liquid absorbency.

  In the final composition of the aqueous gel fragrance, the content of the component (a) is preferably 0.01 to 30% by mass, more preferably 0.1 to 10% by mass, and the content of the component (b) is 0.00. 001-30% by mass, more preferably 0.01-10% by mass, content of component (c) is preferably 0.1-50% by mass, more preferably 0.5-20% by mass, content of component (d) The amount is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, and the water content is preferably 50 to 99% by mass, and more preferably 70 to 90% by mass.

  The aqueous gel fragrance of the present invention is prepared as a gel-like product containing the component (a), the component (b), the component (c) and the component (d). Well-known methods used for the production of general gel-like aroma / deodorants, foods, pharmaceutical gel-like compositions and the like can be widely employed. In the present invention, a method in which the liquid mixture according to the present invention is absorbed to swell the component (d) and gel is suitable.

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

  In the present invention, the container in which the aqueous gel fragrance is accommodated can contain the aqueous gel fragrance and has an open portion, from which the fragrance / deodorant component [(( As long as the component b) can be volatilized, the shape and structure thereof are not particularly limited, and those having an open part at the top and those at the other part such as a side part can be used.

  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 from a slit or an opening is preferable. Furthermore, plastic containers conventionally used for fragrances and deodorants, specifically containers such as polyethylene terephthalate (PET), polypropylene, polyethylene, and polystyrene are preferably used.

  Further, the container can be provided with a contrasting color on the inner wall of the container and the aqueous gel fragrance so that the shrinkage (reduction) of the aqueous gel fragrance can be clearly seen as needed.

  In the present invention, the aqueous gel fragrance may be housed in a refillable simple container. The water-based gel air freshener contained in the simple container is housed in the airtight container in a sealed state. For example, when the water-based gel air freshener installed and used reaches the end of use, the container is opened. The aqueous gel fragrance contained in the simple container can be transferred to another container for installation and used.

  In this case, the container containing the aqueous gel fragrance may be a simple refilling container such as a thin-walled bottle or a pouch. For thin bottles, materials such as polyethylene terephthalate (PET), polypropylene, and polyethylene are preferable, and for pouches, films such as PET, polypropylene, polyethylene, nylon, and aluminum laminates of these plastics, aluminum deposition, and silica deposition are preferable. .

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

  The water-based gel air freshener of the present invention shrinks the gel-like product due to evaporation of water and various components from the water-based air freshener over time by use, and the residual when this shrinkage reaches the critical is the initial mass (use Less than 20% of the mass in the container at the start). Therefore, for example, by visually checking the contraction state of the composition over time from the outside of the container, the end point of use and the replacement time of the fragrance deodorant composition can be easily determined. can do.

  The expression mechanism of the sustained-release effect of the fragrance component in the aqueous gel fragrance of the present invention is not completely elucidated, but when the liquid mixture containing the silicone compound and the fragrance is absorbed in the water absorbent resin, the water absorption It can be expected that the silicone compound which is considered to be hardly absorbed in the resin exists in a state of being coated on the gel surface. On the other hand, the behavior of the fragrance component during liquid absorption is such that a particularly hydrophilic fragrance component is absorbed in water-absorbing resin in a dissolved or dispersed state, and a relatively hydrophobic fragrance is In the dispersed state, it is considered to be present in the silicone layer that is absorbed in the water absorbent resin or formed in the vicinity of the gel surface. The use of the surfactant is considered to contribute to the uniform and stable dispersion of the fragrance component and the silicone compound in the aqueous solution, and to create the above-described aqueous gel state uniformly. When the fragrance component is volatilized from the aqueous gel fragrance in such a form, the fragrance component in the aqueous gel volatilizes from the gel as the water volatilizes, but is more hydrophobic than water when passing through the silicone layer on the gel surface. It is considered that the sustained release effect of the present invention was expressed by adsorption or dissolution because of its high value. Furthermore, the highly hydrophobic fragrance component that is considered to exist in the silicone layer on the gel surface has a stronger interaction with silicone than volatilization from an aqueous system, and the rate of volatilization is reduced, so that the sustained release effect of the present invention is shown. Conceivable. Also, as shown in the examples below, when silicone is present in an aqueous gel, it exhibits a higher sustained release effect of the fragrance. Therefore, in the aqueous gel fragrance of the present invention, the fragrance and the silicone are fragrance on the gel surface. Since it passes through the high-concentration silicone layer at the time of volatilization, it is considered that a high interaction occurred due to the concentration effect and the like as compared with the dispersion or solution of silicone and fragrance without using the water-absorbent resin. As a result, it is considered that (b) the fragrance component can be gradually released over a long period of time.

The components used in Examples and Comparative Examples are shown below.
a-1: Polyether-modified silicone (FZ2101 viscosity 7000 mm ² / s (25 ° C.), Toray Dow Corning Co., Ltd.)
a-2: amino-modified silicone (BY16-872, viscosity 20000 mm ² / s (25 ° C.), functional group equivalent 1800, Toray Dow Corning Co., Ltd.)
a-3: Amino-polyether modified silicone (BY16-893, viscosity 500 mm ² / s (25 ° C.), functional group equivalent 4000, Toray Dow Corning Co., Ltd.)
a-4: Polyether-modified silicone (FZ2105, viscosity: 3500 mm ² / s (25 ° C.), Toray Dow Corning Co., Ltd.)
a-5: Polyether-modified silicone (SH3749 FLUID viscosity 1200 mm ² / s (25 ° C.), Toray Dow Corning Co., Ltd.
a-6: Polyether-modified silicone (FZ2105, viscosity: 50 mm ² / s (25 ° C.), Toray Dow Corning Co., Ltd.)
a-7: Polyether-modified silicone (SH3771M viscosity 320 mm ² / s (25 ° C.), Toray Dow Corning Co., Ltd.)
a-8: polyether-modified silicone (FZ2207, viscosity 3500 mm ² / s (25 ° C.), Toray Dow Corning Co., Ltd.)
a-9: Polyether-modified silicone (FZ2208, viscosity 20000 mm ² / s (25 ° C.), Toray Dow Corning Co., Ltd.)
a-10: Dimethicone emulsion (BY22-029 Toray Dow Corning Co., Ltd.)
a-11: Dimethicone emulsion (BY22-060 Toray Dow Corning Co., Ltd.)
a-12: Dimethicone emulsion (7-3100 GUM Toray Dow Corning Co., Ltd.)

b-1: Fragrance containing 61% by mass of ClogP = 1 to 4 fragrance compounds (ClogP = 1 to less than 2 is 3% by mass, ClogP = 2 to less than 3 is 35% by mass, ClogP = 3 to 4 is 23% by mass %)
b-2: methyl benzoate, log P = 2.111

c-1: Polyoxyethylene lauryl ether (average number of moles of added ethylene oxide 9)

d-1: Acrylamide-acrylic acid (salt) copolymer (HIISOB Aiei Precision Chemical Co., Ltd.)
d-2: Cross-linked polyacrylic acid (Aquaric CA H2, manufactured by Nippon Shokubai Co., Ltd.)
d-3: Cross-linked product of isobutylene-maleic anhydride copolymer (Aqua Beads-M, manufactured by Kuraray Trading Co., Ltd.)
e-1: Dipropylene glycol

Example 1 and Comparative Example 1
Put 2.0 g of the liquid mixture of Table 1 and 0.1 g of the d-1 component prepared using the blending components of Table 1 into a wide-mouth standard bottle (PS-No. 6), close the lid, and liquid the d-1 component. The mixture was allowed to absorb (96 hours) to produce an aqueous gel fragrance. About this aqueous gel fragrance | flavor, the lid | cover of the wide-mouth standard bottle was opened and volatilized simultaneously in a thermostatic chamber of 20 degreeC65%, and the time when the fragrance disappeared was measured. In addition, the time when the fragrance disappeared was similarly measured for 2.0 g of the liquid mixture shown in Table 1 as it was put in the wide-mouth standard bottle (PS-No. 6) without absorbing the d-1 component. did. The results are shown in Table 1.

  From the results of Table 1, the effect (the degree of improvement in scent sustainability) when the silicone compound is added to the fragrance can be greater due to the presence of the water-absorbing resin (d) component as in Example 1. Recognize.

Example 2 and Comparative Example 2
(Gel preparation methods of Examples 2-1 to 2-13 and Comparative Examples 2-1 to 2-3)
An aqueous gel air freshener was prepared by putting 90 g of the liquid mixture of Table 2 prepared using the blending components of Table 2 and 3.0 g of the d-2 component into a wide-mouth standard bottle (PS-No. 13) and mixing them.

(Gel preparation method of Example 2-14 and Comparative Example 2-4)
An aqueous gel fragrance was prepared by putting 10 g of the liquid mixture of Table 2 prepared using the blending components of Table 2 and 1.0 g of the d-2 component into a wide-mouth standard bottle (PS-No. 6) and mixing them.

(Gel preparation method of Example 2-15 and Comparative Example 2-5)
An aqueous gel fragrance was prepared by putting 100 g of the liquid mixture of Table 2 prepared using the blending components of Table 2 and 1.0 g of the d-2 component into a wide-mouth standard bottle (PS-No. 13) and mixing them.

(Evaluation method)
1.0 g of the produced aqueous gel fragrance was placed in a wide mouth standard bottle (PS-No. 6). The lid of the wide-mouth standard bottle was opened in a temperature-controlled room at 20 ° C. and 65%, and vaporized for 96 hours. After volatilization, six evaluators performed fragrance evaluation with the aqueous gel fragrance before volatilization and the following evaluation criteria. The average value of 6 people is shown in Table 2. If this average value is 3 or more, it can be said that the sustained release effect is recognized.
* Evaluation standard 5 of scent intensity: The scent is felt very strongly with an intensity equal to or higher than the initial value (immediately after production).
4: Although slightly weaker than the initial stage (immediately after production), the scent is felt strongly.
3: It is weaker than the initial stage (immediately after production), but feels fragrance.
2: It is considerably weaker than the initial stage (immediately after production) and has a faint scent.
1: There is almost no fragrance.

Example 3
Put 2.0 g of the liquid mixture of Table 3 prepared using the ingredients of Table 3 and 0.1 g of the water absorbent resin of Table 3 in a wide-mouth standard bottle (PS-No. 6), close the lid, The liquid mixture was absorbed (96 hours) to produce an aqueous gel fragrance. The produced aqueous gel fragrance was volatilized for 96 hours by opening the lid of a wide-mouth standard bottle in a thermostatic chamber at 20 ° C. and 65%. After volatilization, in the same manner as in Example 2, the sustained release effect was evaluated based on the evaluation score. The results are shown in Table 3.

Claims (8)

(A) one or more silicone compounds selected from dimethyl silicone, polyether-modified silicone, and amino-modified silicone , (b) perfume, (c) a nonionic surfactant represented by the following general formula (c1), d) An aqueous gel fragrance containing a water-absorbent resin and water, wherein the water content is 50 to 99 % by mass.
R—O— (AO) _n —H (c1)
[Wherein, R is an alkyl group or alkenyl group having 8 to 24 carbon atoms, AO is at least one selected from ethylene oxide and propylene oxide, and the addition form may be random addition or block addition. N represents the average number of moles added, and n = 2-100. ] (A) One or more silicone compounds selected from dimethyl silicone, polyether-modified silicone, and amino-modified silicone , (b) perfume, (c) nonionic surfactant represented by the following general formula (c1) and water A water-based gel air freshener comprising a liquid mixture containing a water-soluble resin and (d) a water-absorbent resin, wherein the water content is 50 to 99 % by mass.
R—O— (AO) _n —H (c1)
[Wherein, R is an alkyl group or alkenyl group having 8 to 24 carbon atoms, AO is at least one selected from ethylene oxide and propylene oxide, and the addition form may be random addition or block addition. N represents the average number of moles added, and n = 2-100. ] The aqueous gel fragrance according to claim 1 or 2 , wherein (b) is a fragrance containing 50 to 100% by mass of a fragrance compound having log P = 1 to 4. (D) is a water absorbent resin selected from a water absorbent resin having acrylic acid and / or a neutralizing group thereof as a structural unit, and a water absorbent resin crosslinked with a copolymer having isobutylene and maleic anhydride as a structural unit. The aqueous gel fragrance according to any one of claims 1 to 3 . The aqueous gel fragrance according to any one of claims 1 to 4 , comprising (a) 0.01 to 30% by mass and (b) 0.001 to 30% by mass. The aqueous gel fragrance according to any one of claims 1 to 5 , wherein the mass ratio of (a) to (b) is (a) / (b) and is 1000/1 to 1/100. The aqueous gel fragrance according to any one of claims 1 to 6 , wherein the mass ratio of (a) to (d) is 10/1 to 1/100 in terms of (a) / (d). A stationary fragrance comprising the aqueous gel fragrance according to any one of claims 1 to 7 .