JPH0332673A - Gelatinous aromatic agent composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention provides a method for preparing a fragrance-containing liquid mixture in an aqueous gel composition that can uniformly volatilize water, which is a fragrance volatilization carrier, and can emit a fragrance continuously over a long period of time. and/or a novel gel-like fragrance composition in which capsules containing a core material made of a fragrance-impregnated solid are dispersed.

BACKGROUND OF THE INVENTION Conventionally, gel-like fragrances are known as aqueous gel-type fragrances formed using water as a solvent and agar or carrageenan as a gelling agent (Japanese Patent Publication No. 55-1812).
No. 70532/1983, Japanese Patent Application Laid-Open No. 1987-70532
No. 57451), and an oil-based gel type aromatic agent formed using a terpene hydrocarbon as a solvent and soap as a gelling agent (Japanese Patent Laid-Open No. 53-9114).
9, JP-A-56-89261, JP-A-60
-53148, JP-A-61-43107)
is known, but the majority of commercially available gelter ops are water-based. However, since this aqueous gel type is simply an emulsified dispersion of non-water soluble fragrances as oil droplets in an aqueous gel, the ingredients that are easily volatile during use will evaporate preferentially, resulting in The drawback is that the quality and strength of the fragrance change significantly depending on the taste.

Therefore, there is a method of coating the aqueous gel surface with an organic liquid to delay volatilization (Japanese Unexamined Patent Publication No. 55-38166), and a method of improving the components of the gel composition to impart sustainability (Japanese Patent Publication No. 55-38166).
Although improvement methods such as Japanese Patent No. 8-34142) have been proposed, none of them are sufficiently effective, and as a method to maintain a constant fragrance quality and aroma over a long period of time,
This cannot necessarily be said to be satisfactory.

On the other hand, it is also known to incorporate fragrances into microcapsules for the purpose of prolonging the fragrance (Japanese Patent Application Laid-Open No. 1989-1999).
-5540, Japanese Patent Application Laid-open No. 58-143760)
, these are for use in plastics and are not related to fragrances.

The gelling agents of these aqueous gels are mainly formulated as excipients for fragrance ingredients, so they do not take into consideration the volatility of water, which is the carrier of fragrance ingredients. However, the release of water from the aqueous gel is difficult to control, and the water containing the fragrance is easily released, and the highly volatile fragrance ingredients in particular evaporate faster than the aqueous gel, causing the fragrance to disappear in a short period of time. However, it still has the disadvantage that it varies significantly.

In addition, an aqueous gel using carrageenan and (-carrageenan) as a gelling agent has been proposed (Japanese Patent Laid-Open No. 6
3-291545), these are aqueous gels for food or cosmetics, and their field of use and purpose are different from the usual uses of gel air fresheners, such as toilets, automobiles, indoors, and bathrooms. Even if aqueous gel fragrances are prepared by blending these gelling agents with fragrances, there is a problem in that it is difficult to continuously release fragrances over a long period of time.

Problems to be Solved by the Invention The present invention provides a gel-like fragrance that can be used continuously over a long period of time with constant fragrance quality and intensity even when a compound fragrance consisting of many types of fragrance ingredients is used. It was made for the purpose of providing a composition.

Means for Solving the Problems As a result of intensive research to develop a gel-like fragrance composition that can continuously release a constant fragrance over a long period of time, the present inventors discovered that water, which is a fragrance carrier, The flavor-containing liquid mixture and/or the flavor-containing liquid mixture and/or
Alternatively, the inventors discovered that the objective could be achieved by dispersing and blending capsules containing a core material made of a solid perfume-impregnated substance, and based on this knowledge, the present invention was completed.

That is, the present invention provides an aqueous gel-like composition comprising a gelling agent, a gelling agent, and a surfactant, which has an average particle size of 0 and contains a core material consisting of a perfume-containing liquid mixture and/or a perfume-impregnated solid in the gel. The present invention provides a gel-like fragrance composition characterized in that capsules having a wing size of 1 to 1000 μm are dispersed therein.

The present invention will be explained in detail below.

The gelling agent used in the composition of the present invention is one that can form an aqueous gel that can uniformly volatilize water as a carrier for perfume, and usually has a strong affinity for water and a dense gel network structure. There is.

Typical gelling agents include natural gelling agents such as Ni-carrageenan, C-carrageenan, locust bean gum, polyvinylpyrrolidone, polyvinyl methacrylate, polyvinyl methyl ether, polyvinyl alcohol, and acetoacetyl. Vinyl polymers such as PVA or derivatives thereof, polyacrylic acid,
its salts, polyacrylic esters, copolymers thereof,
Examples include synthetic thread gelling agents such as crosslinked acrylic acid polymers, acrylic polymers such as their salts, and urethane polymers having urethane bonds made from polyols and incyanate derivatives, among which - Carrageenan, a combination system of two or more of 1 to carrageenan and locust bean gum, a urethane polymer made from a hydrophilic polyol and an isocyanate derivative,
Acedoacetylated PVA is preferred.

The blending amount of these is usually 0.5 to 20% by weight based on the total amount,
It is preferably selected in a range of 1 to 15% by weight. If the amount is less than 0.5% by weight, the gel-forming portion will be reduced, and if it is more than 20% by weight, no particular improvement in effect can be expected and it is not economical.

Examples of the surfactant used in the present invention include nonionic surfactants such as sorbitan fatty acid esters, ethylene oxide adducts thereof, ethylene oxide adducts of alkylphenols such as nonylphenol, ethylene oxide adducts of higher alcohols, and ethylene oxide adducts of secondary alcohols. activator, alkylbenzene sulfonate,
Anionic surfactants such as σ-olefin sulfonate are used. These may be used alone or
Also, two or more types may be used in combination.

The blending amount of these components is usually selected within the range of 0.1 to 20% by weight, preferably 0.5 to 10% by weight.

Examples of fragrances used in the present invention include σ-pinene, β-
Terpene hydrocarbons such as pinene, myrcene, limonene, l,8-cineole, amyl acetate, amyl propionate, prenylacetate, hexyl acetate, cis-3-hexenyl acetate, allyl caproate, tetrahydrolinalyl Acetate, ethyl caproate, ethyl butyrate, ethyl acetoacetate, allylisoamyloxyacetate, ethylmethylphenyl glycolate, ethyl-p-methyl-β-phenyl glycolate, benzyl acetate, bornyl acetate, pt-butyl Cyclohexyl acetate, o-
Esters such as t-butylcyclohexyl acetate, cedryl acetate, methyl dihydrojasmonate, linalyl acetate, aliphatic aldehydes having 6 to 13 carbon atoms, benzaldehyde, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde , a-n-amyl cinnamic aldehyde, a-n-hexyl cinnamic aldehyde, lyaldehyde, lyral, miracualdehyde, citral, aldehydes such as cyclamen aldehyde, γ-nonalactone, γ-decalactone, γ-un Decalactone, δ-nonalactone, δ-
Lactones such as decalactone, δ-undecalactone, ionones, ketones such as methylionone, alcohols such as linalool, tetrahydrolinalool, β-phenylethyl alcohol, geraniol, citronellol, lemon oil, orange oil, lime oil Essential oils such as , eucalyptus oil, cypress oil, cypress oil, pine oil, turpentine oil, horse oil, lavender oil, jasmine oil, vanilla, peppermint, and spearmint are used. These may be used alone or in combination of two or more.

The capsules used in the present invention are produced by a known method such as an interfacial polymerization method, an in-situ polymerization method, a phase separation method, or an in-liquid curing method, using a perfume-containing liquid mixture and a perfume-impregnated solid as core materials. can do.

It is preferable to use a solvent with a high boiling point, a solvent with a low vapor pressure, or the like in the perfume-containing liquid mixture in order to uniformly dissolve the mixed perfume ingredients and release the perfume slowly.

Examples of such solvents include ethylene glycol,
Examples include glycols such as fluorene glycol, ethylene glycol monoethyl ether, and diethylene glycol monobutyl ether, heptathalic acid esters such as diethyl phthalate, benzyl benzoate, santalol, benzyl benzoate, and diisobutyl adipate.

The fragrance-impregnated solid is not particularly limited as long as it can impregnate the surface and inner surface of the solid with the fragrance, and any solid can be used. Examples of such solids include cellulose polymers such as ethyl cellulose, nitrocellulose, cellulose acetate butyrate, and cellulose acetate propionate; petroleum polymers such as polybutadiene, chloroprene rubber, butyl rubber, silicone rubber, and polyisobutylene; Vinyl chloride, polystyrene, polyvinyl acetate, polymethacrylate ester, polycaglolactone, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-divinylbenzene copolymer,
Examples include organic impregnated solids such as vinyl, acrylic or styrenic polymers such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, butadiene-acrylonitrile copolymer, and inclusion compounds such as cyclodextrin. . In addition, inorganic porous bodies and inorganic powders such as silica, zeolite, synthetic leather silicates such as aluminum silicate, and montmorillonite clay minerals are exemplified as the inorganic impregnated solid.

These materials may be crosslinked with a suitable crosslinking agent in order to incorporate fragrances, or may be used as they are if they themselves absorb fragrances or are porous.

Examples of capsule membrane materials include polyamide, polyester, polyurea, epoxy resin, polyurethane, polysulfonate, etc. for interfacial polymerization, and urea-formaldehyde resin, polyurethane, acrylic resin, etc. for in-situ polymerization. Polyvinyl acetate, polystyrene, styrene-isobutylene copolymer, etc. In the case of phase separation method, gelatin, a mixture of gelatin and gum arabic or polysaccharide derivatives, polyvinyl alcohol, water-soluble nylon, sulfated cellulose, methylcellulose, etc. In the case of the medium curing method, alginic acid, pectin, polyvinyl alcohol, etc. are used. Note that the capsules prepared by the phase separation method or the in-liquid curing method can be further subjected to a curing treatment, if necessary.

As the fragrance contained in this capsule, those mentioned above as examples of the fragrance contained in the gel base can be used, but among these, particularly preferred are 2.
The vapor pressure at 5° C. is 30 μm Hg or more.

In the composition of the present invention, the fragrance may be blended entirely in the capsule, or may be blended separately into the aqueous gel and capsule. When compounding the fragrance separately in the aqueous gel and in the capsule, the fragrance may be the same as or different from the fragrance contained in the aqueous gel, but when using a blended fragrance, more It is advantageous to have a built-in fragrance containing a large amount of volatile components in order to maintain a constant fragrance quality.

In addition to the above-mentioned components, the composition of the present invention may optionally contain ethylene-, di-, or tri-ethylene glycols such as di-, di-, or tri-ethylene glycol yapropylene glycol, ethylene glycol ethyl ether, diethylene glycol butyl ether, ethylene glycol dimethyl ether, etc. Glycols such as ethylene glycol alkyl ether, thickeners such as locust bean gum, polyvinyl alcohol hydroxypropyl methylcellulose, guar gum, and gum arabic, and additive ingredients commonly used in water-based gel type fragrances, such as colorants and oxidants. inhibitor,
It can contain preservatives, disinfectants, etc.

Next, to explain one example of a preferred method for producing the gel-like fragrance composition of the present invention, first, a gelling agent and additive components such as a thickener, a coloring agent, and a preservative to be used as desired are added to water. The mixture is stirred under heating to dissolve, and then the fragrance and emulsifier are added thereto to homogeneously emulsify and disperse the fragrance, and then cooled to prepare an aqueous gel slurry. After uniformly dispersing capsules containing a core material made of a fragrance-containing liquid mixture and/or a fragrance-impregnated solid in this slurry, the gel-like fragrance composition of the present invention is prepared by pouring into a predetermined container and cooling to gel. can manufacture things.

Effects of the Invention The gel-like fragrance composition of the present invention has excellent characteristics, such as being able to continuously release a constant fragrance over a long period of time, and being able to easily control volatilization of the fragrance.

Therefore, the gel fragrance composition of the present invention is suitable for use in, for example, toilets, automatic military use, indoor use, and the like.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

The physical properties of each gel-like fragrance composition were evaluated according to the following method.

(1) As a test method to accelerate moisture volatilization control, a can with a diameter of 65 m + i% and a height of 30 + m was filled with aqueous gel composition 509, left at 35°C for one week, and when the can was opened, the release from the gel was measured. The moisture content was evaluated according to the following criteria.

O: Almost no free moisture △: Some free moisture ×: Significantly large amount of free moisture (2) Fragrance strength Gel air freshener composition 509 has a diameter of 55 mm and a height of 30 m.
Fill a can into a can, leave it at room temperature for 24 hours, then open the can (
I used an initial sample that was fully opened. Furthermore, this sample was left at 25°C for 1 week and 2 weeks to be used as a sustainable sample. To evaluate the strength of the scent, the sample was placed in an order box of approximately 2.51 mm, and the strength was sensory-evaluated 20 minutes later. For the evaluation score, the initial sample of each composition was used as a standard, and the average value of four judges was adopted.

4 points: Stronger than the standard product 3 points: Same as the standard product 2 points: Slightly weaker than the standard product 1 point: Weaker than the standard product First, capsules with built-in fragrance were prepared as in the following reference example.

Reference Example 1 6 g of terephthalic acid chloride is added and dissolved in a predetermined fragrance-containing liquid mixture 1009, and this is poured into water 1259 while stirring to be dispersed. Then, after cooling to about 5°C and adding the required amount of sodium hydroxide,
By adding 0% hexamethylene diamine aqueous solution 17.59 to perform interfacial polymerization, polyhexamethylene
Microcapsules (1) having an average particle size of 50 μm were obtained by encapsulation with a talamide membrane.

The perfume-containing liquid mixture is a mixture of 80% by weight of the lemon-based blended perfume described in Table 1 Note) and 1 to 20% by weight of benzylbenzony.

Reference Example 2 Nylon-6,
10 membranes to obtain microcapsules (It) with an average particle size of 30 μm.

Reference Example 3 Microcapsules (III) having an average particle size of 50 μm were obtained by encapsulation with a polyester film in the same manner as in Reference Example 1 except that bisphenol A was used in place of hexamethylene diamine.

Reference Example 4 Microcapsules were produced by a phase separation method using gelatin and gum arabic as film-forming components, and then hardened with glutaraldehyde to encapsulate them with a hardened gelatin film to produce microcapsules with an average particle size of 70 μm ( IV) was obtained.

Reference example 5 Flavoring ingredient Blending amount (weight%) Linalool 20 hexenol
3 hexyl alcohol 10
Benzyl alcohol 27 Methyl ionone 10γ-decalactone
lO roseus lO jasmine base 10 The above osmanthus-based blended fragrance (b) 159 was impregnated into 10 g of styrene-divinylbenzene cross-linked polymer beads (Diaion lP2O, manufactured by Mitsubishi Kasei Corporation), and encapsulated with a 6-T nylon membrane by an interfacial polymerization method. , spherical sustained-release capsules (V) with an average particle diameter of 300 μm were obtained.

Reference Example 6 The osmanthus-based blended fragrance (b) 259 was impregnated into a styrene-based hydrophobic adsorption resin (Duoly I-S-861; manufactured by Sumitomo Chemical Co., Ltd.) L09, and encapsulated with a 6-T nylon membrane by an interfacial polymerization method. , spherical sustained-release capsules (Vl) with an average particle size of 500 μm were obtained.

Reference Example 7 10 h of a fragrance-containing liquid mixture was prepared by adding log benzyl benzoate to 90 g of the osmanthus-based blended fragrance (b), and then interfacial polymerization was carried out in the same manner as in Reference Example 1 to form a polyhexamethylene 7-talamide film. The mixture was encapsulated to obtain microcapsules (■) with an average particle size of 30 μm.

Reference Example 8 After preparing 100 g of a fragrance-containing liquid mixture by adding diisobutyl adipate log and benzyl benzoate log to 80 g of the osmanthus-based blended fragrance (b), interfacial polymerization was performed in the same manner as in Reference Example 2 to obtain nylon-6. , was encapsulated with a 1O film to obtain microcapsules (■) with an average particle size of 50 μm.

Reference Example 9 10 g of diisobutyl adipate was added to 90 g of the osmanthus-based blended fragrance (b) to prepare 100 g of a fragrance-containing liquid mixture.
After preparing 9, 10 g of this was impregnated with 10 g of finely powdered silicic acid (Shizukashiru P802, manufactured by Suiko Kagaku Kogyo Co., Ltd.), and encapsulated with a 6-T nylon membrane using an interfacial polymerization method. Release capsules ([) were obtained.

Examples 1 to 7, Comparative Example 1.2 - 2.0% by weight of carrageenan, 0.0% by weight of carrageenan.
2% by weight, locust bean gum 0.41t%, ethylene glycol 1.0% by weight, propylene glycol z,
omt%, diethylene glycol ethyl ether 1.0
Weight%, Softanol 400 (manufactured by Nippon Shokubai Chemical Co., Ltd.,
C1□~, linear secondary alcohol E040 mole adduct)
1.0% by weight, preservative 0.1% by weight, antioxidant 0. l
An aqueous gel-like composition was prepared from the fragrance in the proportions shown in Table 1, and the balance was water. On the other hand, Table 1 shows the results of a test on the persistence of fragrance intensity depending on the presence or absence of fragrance capsules in the reference example.

Examples 8 to 17 Gelling agent and surfactant in the proportions shown in Table 2, preservative 0
．． 1% by weight, antioxidant 0.1% by weight, colorant 0.05
A gel fragrance composition was prepared by separately blending the above-mentioned osmanthus-based blended fragrance (b) into a gel and a capsule into an aqueous gel composition consisting of % by weight and the balance being water. Table 2 shows the results of tests on the controllability of moisture volatilization and the persistence of fragrance intensity.

Description 11 Title of the invention Gel-like fragrance composition 2, Claims 1 An aqueous gel-like composition comprising a gelling agent and a gelling agent and a surfactant, wherein the gel contains a fragrance-containing liquid mixture and/or A gel-like fragrance composition characterized in that capsules having an average particle size of 0.1 to 1000 μm and containing a core material made of a fragrance-impregnated solid are dispersed therein.

2 Acetoacetylated PV, a urethane polymer whose gelling agent is made from a hydrophilic polyol and an isocyanate derivative
The gel fragrance composition according to claim 1 or 2, which is a combination system of two or more of A-carrageenan, C-carrageenan, and locust bean gum.

3. The weight ratio of I-carrageenan and I-carrageenan in the aqueous gel composition is 1/t=1/1 to 50.
The gel-like fragrance composition according to claim 1.2 or 3, wherein the amount is /l.

3. Detailed Description of the Invention Industrial Field of Application The present invention provides a fragrance-containing liquid mixture in an aqueous gel-like compound that can uniformly volatilize water, which is a fragrance volatilization carrier, and can emit a fragrance continuously over a long period of time. and/or a novel gel-like fragrance composition in which capsules containing a core material made of a fragrance-impregnated solid are dispersed.

BACKGROUND OF THE INVENTION Conventionally, gel-like fragrances are known as aqueous gel-type fragrances formed using water as a solvent and agar or carrageenan as a gelling agent (Japanese Patent Publication No. 55-1812).
No. 70532/1983, Japanese Patent Application Laid-Open No. 1987-70532
No. 57451), and an oil-based gel type aromatic agent formed using a terpene hydrocarbon as a solvent and soap as a gelling agent (Japanese Patent Laid-Open No. 53-9114).
9, JP-A-56-89261, JP-A-60
-53148, JP-A-61-43107)
is known, but the majority of commercially available gelter ops are water-based. However, since this aqueous gel type is simply an emulsified dispersion of non-water soluble fragrances as oil droplets in an aqueous gel, the ingredients that are easily volatile during use will evaporate preferentially, resulting in The drawback is that the quality and strength of the fragrance change significantly depending on the taste.

Therefore, there is a method of coating the aqueous gel surface with an organic liquid to delay volatilization (Japanese Unexamined Patent Publication No. 55-38166), and a method of improving the components of the gel composition to impart sustainability (Japanese Patent Publication No. 55-38166).
Although improvement methods such as Japanese Patent No. 8-34142) have been proposed, none of them are sufficiently effective, and as a method to maintain a constant fragrance quality and aroma over a long period of time,
This cannot necessarily be said to be satisfactory.

On the other hand, it is also known to incorporate fragrances into microcapsules for the purpose of prolonging the fragrance (Japanese Patent Application Laid-Open No. 1989-1999).
-5540, Japanese Patent Application Laid-open No. 58-143760)
, these are for use in plastics and are not related to fragrances.

The gelling agents of these aqueous gels are mainly formulated as excipients for fragrance ingredients, so they do not take into consideration the volatility of water, which is the carrier of fragrance ingredients. However, the release of water from the aqueous gel is difficult to control, and the water containing the fragrance is easily released, and the highly volatile fragrance ingredients in particular evaporate faster than the aqueous gel, causing the fragrance to disappear in a short period of time. However, it still has the disadvantage that it varies significantly.

In addition, an aqueous gel using carrageenan and (-carrageenan) as a gelling agent has been proposed (Japanese Patent Laid-Open No. 6
3-291545), these are aqueous gels for food or cosmetics, and their field of use and purpose are different from the usual uses of gel air fresheners, such as toilets, automobiles, indoors, and bathrooms. Even if aqueous gel fragrances are prepared by blending these gelling agents with fragrances, there is a problem in that it is difficult to continuously release fragrances over a long period of time.

Problems to be Solved by the Invention The present invention provides a gel-like fragrance that can be used continuously over a long period of time with constant fragrance quality and intensity even when a compound fragrance consisting of many types of fragrance ingredients is used. It was made for the purpose of providing a composition.

Means for Solving the Problems As a result of intensive research to develop a gel-like fragrance composition that can continuously release a constant fragrance over a long period of time, the present inventors discovered that water, which is a fragrance carrier, The flavor-containing liquid mixture and/or the flavor-containing liquid mixture and/or
Alternatively, the inventors discovered that the objective could be achieved by dispersing and blending capsules containing a core material made of a solid perfume-impregnated substance, and based on this knowledge, the present invention was completed.

That is, the present invention provides an aqueous gel-like composition comprising a gelling agent, a gelling agent, and a surfactant, which has an average particle size of 0 and contains a core material consisting of a perfume-containing liquid mixture and/or a perfume-impregnated solid in the gel. The present invention provides a gel-like fragrance composition characterized in that capsules having a wing size of 1 to 1000 μm are dispersed therein.

The present invention will be explained in detail below.

The gelling agent used in the composition of the present invention is one that can form an aqueous gel that can uniformly volatilize water as a carrier for perfume, and usually has a strong affinity for water and a dense gel network structure. There is.

Typical gelling agents include natural gelling agents such as Ni-carrageenan, C-carrageenan, locust bean gum, polyvinylpyrrolidone, polyvinyl methacrylate, polyvinyl methyl ether, polyvinyl alcohol, and acetoacetyl. Vinyl polymers such as PVA or derivatives thereof, polyacrylic acid,
its salts, polyacrylic esters, copolymers thereof,
Examples include synthetic thread gelling agents such as crosslinked acrylic acid polymers, acrylic polymers such as their salts, and urethane polymers having urethane bonds made from polyols and incyanate derivatives, among which - Carrageenan, a combination system of two or more of 1 to carrageenan and locust bean gum, a urethane polymer made from a hydrophilic polyol and an isocyanate derivative,
Acedoacetylated PVA is preferred.

The blending amount of these is usually 0.5 to 20% by weight based on the total amount,
It is preferably selected in a range of 1 to 15% by weight. If the amount is less than 0.5% by weight, the gel-forming portion will be reduced, and if it is more than 20% by weight, no particular improvement in effect can be expected and it is not economical.

Examples of the surfactant used in the present invention include nonionic surfactants such as sorbitan fatty acid esters, ethylene oxide adducts thereof, ethylene oxide adducts of alkylphenols such as nonylphenol, ethylene oxide adducts of higher alcohols, and ethylene oxide adducts of secondary alcohols. activator, alkylbenzene sulfonate,
Anionic surfactants such as σ-olefin sulfonate are used. These may be used alone or
Also, two or more types may be used in combination.

The blending amount of these components is usually selected within the range of 0.1 to 20% by weight, preferably 0.5 to 10% by weight.

Examples of fragrances used in the present invention include σ-pinene, β-
Terpene hydrocarbons such as pinene, myrcene, limonene, l,8-cineole, amyl acetate, amyl propionate, prenylacetate, hexyl acetate, cis-3-hexenyl acetate, allyl caproate, tetrahydrolinalyl Acetate, ethyl caproate, ethyl butyrate, ethyl acetoacetate, allylisoamyloxyacetate, ethylmethylphenyl glycolate, ethyl-p-methyl-β-phenyl glycolate, benzyl acetate, bornyl acetate, pt-butyl Cyclohexyl acetate, o-
Esters such as t-butylcyclohexyl acetate, cedryl acetate, methyl dihydrojasmonate, linalyl acetate, aliphatic aldehydes having 6 to 13 carbon atoms, benzaldehyde, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde , a-n-amyl cinnamic aldehyde, a-n-hexyl cinnamic aldehyde, lyaldehyde, lyral, miracualdehyde, citral, aldehydes such as cyclamen aldehyde, γ-nonalactone, γ-decalactone, γ-un Decalactone, δ-nonalactone, δ-
Lactones such as decalactone, δ-undecalactone, ionones, ketones such as methylionone, alcohols such as linalool, tetrahydrolinalool, β-phenylethyl alcohol, geraniol, citronellol, lemon oil, orange oil, lime oil Essential oils such as , eucalyptus oil, cypress oil, cypress oil, pine oil, turpentine oil, horse oil, lavender oil, jasmine oil, vanilla, peppermint, and spearmint are used. These may be used alone or in combination of two or more.

The capsules used in the present invention are produced by a known method such as an interfacial polymerization method, an in-situ polymerization method, a phase separation method, or an in-liquid curing method, using a perfume-containing liquid mixture and a perfume-impregnated solid as core materials. can do.

It is preferable to use a solvent with a high boiling point, a solvent with a low vapor pressure, or the like in the perfume-containing liquid mixture in order to uniformly dissolve the mixed perfume ingredients and release the perfume slowly.

Examples of such solvents include ethylene glycol,
Examples include glycols such as fluorene glycol, ethylene glycol monoethyl ether, and diethylene glycol monobutyl ether, heptathalic acid esters such as diethyl phthalate, benzyl benzoate, santalol, benzyl benzoate, and diisobutyl adipate.

The fragrance-impregnated solid is not particularly limited as long as it can impregnate the surface and inner surface of the solid with the fragrance, and any solid can be used. Examples of such solids include cellulose polymers such as ethyl cellulose, nitrocellulose, cellulose acetate butyrate, and cellulose acetate propionate; petroleum polymers such as polybutadiene, chloroprene rubber, butyl rubber, silicone rubber, and polyisobutylene; Vinyl chloride, polystyrene, polyvinyl acetate, polymethacrylate ester, polycaglolactone, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-divinylbenzene copolymer,
Examples include organic impregnated solids such as vinyl, acrylic or styrenic polymers such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, butadiene-acrylonitrile copolymer, and inclusion compounds such as cyclodextrin. . In addition, inorganic porous bodies and inorganic powders such as silica, zeolite, synthetic leather silicates such as aluminum silicate, and montmorillonite clay minerals are exemplified as the inorganic impregnated solid.

These materials may be crosslinked with a suitable crosslinking agent in order to incorporate fragrances, or may be used as they are if they themselves absorb fragrances or are porous.

Examples of capsule membrane materials include polyamide, polyester, polyurea, epoxy resin, polyurethane, polysulfonate, etc. for interfacial polymerization, and urea-formaldehyde resin, polyurethane, acrylic resin, etc. for in-situ polymerization. Polyvinyl acetate, polystyrene, styrene-isobutylene copolymer, etc. In the case of phase separation method, gelatin, a mixture of gelatin and gum arabic or polysaccharide derivatives, polyvinyl alcohol, water-soluble nylon, sulfated cellulose, methylcellulose, etc. In the case of the medium curing method, alginic acid, pectin, polyvinyl alcohol, etc. are used. Note that the capsules prepared by the phase separation method or the in-liquid curing method can be further subjected to a curing treatment, if necessary.

As the fragrance contained in this capsule, those mentioned above as examples of the fragrance contained in the gel base can be used, but among these, particularly preferred are 2.
The vapor pressure at 5° C. is 30 μm Hg or more.

In the composition of the present invention, the fragrance may be blended entirely in the capsule, or may be blended separately into the aqueous gel and capsule. When compounding the fragrance separately in the aqueous gel and in the capsule, the fragrance may be the same as or different from the fragrance contained in the aqueous gel, but when using a blended fragrance, more It is advantageous to have a built-in fragrance containing a large amount of volatile components in order to maintain a constant fragrance quality.

In addition to the above-mentioned components, the composition of the present invention may optionally contain ethylene-, di-, or tri-ethylene glycols such as di-, di-, or tri-ethylene glycol yapropylene glycol, ethylene glycol ethyl ether, diethylene glycol butyl ether, ethylene glycol dimethyl ether, etc. Glycols such as ethylene glycol alkyl ether, thickeners such as locust bean gum, polyvinyl alcohol hydroxypropyl methylcellulose, guar gum, and gum arabic, and additive ingredients commonly used in water-based gel type fragrances, such as colorants and oxidants. inhibitor,
It can contain preservatives, disinfectants, etc.

Next, to explain one example of a preferred method for producing the gel-like fragrance composition of the present invention, first, a gelling agent and additive components such as a thickener, a coloring agent, and a preservative to be used as desired are added to water. The mixture is stirred under heating to dissolve, and then the fragrance and emulsifier are added thereto to homogeneously emulsify and disperse the fragrance, and then cooled to prepare an aqueous gel slurry. After uniformly dispersing capsules containing a core material made of a fragrance-containing liquid mixture and/or a fragrance-impregnated solid in this slurry, the gel-like fragrance composition of the present invention is prepared by pouring into a predetermined container and cooling to gel. can manufacture things.

Effects of the Invention The gel-like fragrance composition of the present invention has excellent characteristics, such as being able to continuously release a constant fragrance over a long period of time, and being able to easily control volatilization of the fragrance.

Therefore, the gel fragrance composition of the present invention is suitable for use in, for example, toilets, automatic military use, indoor use, and the like.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

The physical properties of each gel-like fragrance composition were evaluated according to the following method.

(1) As a test method to accelerate moisture volatilization control, a can with a diameter of 65 m + i% and a height of 30 + m was filled with aqueous gel composition 509, left at 35°C for one week, and when the can was opened, the release from the gel was measured. The moisture content was evaluated according to the following criteria.

O: Almost no free moisture △: Some free moisture ×: Significantly large amount of free moisture (2) Fragrance strength Gel air freshener composition 509 has a diameter of 55 mm and a height of 30 m.
Fill a can into a can, leave it at room temperature for 24 hours, then open the can (
I used an initial sample that was fully opened. Furthermore, this sample was left at 25°C for 1 week and 2 weeks to be used as a sustainable sample. To evaluate the strength of the scent, the sample was placed in an order box of approximately 2.51 mm, and the strength was sensory-evaluated 20 minutes later. For the evaluation score, the initial sample of each composition was used as a standard, and the average value of four judges was adopted.

4 points: Stronger than the standard product 3 points: Same as the standard product 2 points: Slightly weaker than the standard product 1 point: Weaker than the standard product First, capsules with built-in fragrance were prepared as in the following reference example.

Reference Example 1 6 g of terephthalic acid chloride is added and dissolved in a predetermined fragrance-containing liquid mixture 1009, and this is poured into water 1259 while stirring to be dispersed. Then, after cooling to about 5°C and adding the required amount of sodium hydroxide,
By adding 0% hexamethylene diamine aqueous solution 17.59 to perform interfacial polymerization, polyhexamethylene
Microcapsules (1) having an average particle size of 50 μm were obtained by encapsulation with a talamide membrane.

The perfume-containing liquid mixture is a mixture of 80% by weight of the lemon-based blended perfume described in Table 1 Note) and 1 to 20% by weight of benzylbenzony.

Reference Example 2 Nylon-6,
10 membranes to obtain microcapsules (It) with an average particle size of 30 μm.

Reference Example 3 Microcapsules (III) having an average particle size of 50 μm were obtained by encapsulation with a polyester film in the same manner as in Reference Example 1 except that bisphenol A was used in place of hexamethylene diamine.

Reference Example 4 Microcapsules were produced by a phase separation method using gelatin and gum arabic as film-forming components, and then hardened with glutaraldehyde to encapsulate them with a hardened gelatin film to produce microcapsules with an average particle size of 70 μm ( IV) was obtained.

Reference example 5 Flavoring ingredient Blending amount (weight%) Linalool 20 hexenol
3 hexyl alcohol 10
Benzyl alcohol 27 Methyl ionone 10γ-decalactone
lO roseus lO jasmine base 10 The above osmanthus-based blended fragrance (b) 159 was impregnated into 10 g of styrene-divinylbenzene cross-linked polymer beads (Diaion lP2O, manufactured by Mitsubishi Kasei Corporation), and encapsulated with a 6-T nylon membrane by an interfacial polymerization method. , spherical sustained-release capsules (V) with an average particle diameter of 300 μm were obtained.

Reference Example 6 The osmanthus-based blended fragrance (b) 259 was impregnated into a styrene-based hydrophobic adsorption resin (Duoly I-S-861; manufactured by Sumitomo Chemical Co., Ltd.) L09, and encapsulated with a 6-T nylon membrane by an interfacial polymerization method. , spherical sustained-release capsules (Vl) with an average particle size of 500 μm were obtained.

Reference Example 7 10 h of a fragrance-containing liquid mixture was prepared by adding log benzyl benzoate to 90 g of the osmanthus-based blended fragrance (b), and then interfacial polymerization was carried out in the same manner as in Reference Example 1 to form a polyhexamethylene 7-talamide film. The mixture was encapsulated to obtain microcapsules (■) with an average particle size of 30 μm.

Reference Example 8 After preparing 100 g of a fragrance-containing liquid mixture by adding diisobutyl adipate log and benzyl benzoate log to 80 g of the osmanthus-based blended fragrance (b), interfacial polymerization was performed in the same manner as in Reference Example 2 to obtain nylon-6. , was encapsulated with a 1O film to obtain microcapsules (■) with an average particle size of 50 μm.

Reference Example 9 10 g of diisobutyl adipate was added to 90 g of the osmanthus-based blended fragrance (b) to prepare 100 g of a fragrance-containing liquid mixture.
After preparing 9, 10 g of this was impregnated with 10 g of finely powdered silicic acid (Shizukashiru P802, manufactured by Suiko Kagaku Kogyo Co., Ltd.), and encapsulated with a 6-T nylon membrane using an interfacial polymerization method. Release capsules ([) were obtained.

Examples 1 to 7, Comparative Example 1.2 - 2.0% by weight of carrageenan, 0.0% by weight of carrageenan.
2% by weight, locust bean gum 0.41t%, ethylene glycol 1.0% by weight, propylene glycol z,
omt%, diethylene glycol ethyl ether 1.0
Weight%, Softanol 400 (manufactured by Nippon Shokubai Chemical Co., Ltd.,
C1□~, linear secondary alcohol E040 mole adduct)
1.0% by weight, preservative 0.1% by weight, antioxidant 0. l
An aqueous gel-like composition was prepared from a fragrance having a li content of % and a blending ratio shown in Table 1, and the balance being water. On the other hand, Table 1 shows the results of a test on the persistence of fragrance intensity depending on the presence or absence of fragrance capsules in the reference example.

Examples 8 to 17 Gelling agent and surfactant in the proportions shown in Table 2, preservative 0
．． 1% by weight, antioxidant 0.1% by weight, colorant 0.05
A gel fragrance composition was prepared in which the above-mentioned osmanthus-based compound fragrance (b) was separately blended into a gel and a capsule into an aqueous gel composition consisting of % by weight and the balance being water. Table 2 shows the results of tests on the controllability of moisture volatilization and the persistence of fragrance intensity.

Claims (1)

[Scope of Claims] 1. In an aqueous gel composition consisting of a gelling agent and a gelling agent and a surfactant, an average particle size in which a core material consisting of a perfume-containing liquid mixture and/or a perfume-impregnated solid is incorporated in the gel. A gel fragrance composition characterized in that capsules of 0.1 to 1000 μm are dispersed therein. 2 Acetoacetylated PV, a urethane polymer whose gelling agent is made from a hydrophilic polyol and an isocyanate derivative
The gel-like fragrance composition according to claim 1 or 2, which is a combination system of two or more of A, κ-carrageenan, iota-carrageenan, and locust bean gum. 3. The gel fragrance composition according to claim 1, wherein the weight ratio of κ-carrageenan and ι-carrageenan in the aqueous gel composition is κ/ι=1/1 to 50/l.